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Survey of n-hexane Part of the LOUS review

Environmental Project No. 1628, 2014

2 Survey of n-hexane

Title:

Survey of n-hexane

Authors and contributors:

Sonja Hagen Mikkelsen, Marlies Warming; COWI A/S, Denmark

Jytte Syska, Al Voskian; Syska Consulting

Published by:

The Danish Environmental Protection Agency

Strandgade 29

1401 Copenhagen K

Denmark

www.mst.dk/english

Year:

2014

ISBN no.

978-87-93283-41-1

Disclaimer:

When the occasion arises, the Danish Environmental Protection Agency will publish reports and papers concerning re-

search and development projects within the environmental sector, financed by study grants provided by the Danish Envi-

ronmental Protection Agency. It should be noted that such publications do not necessarily reflect the position or opinion

of the Danish Environmental Protection Agency.

However, publication does indicate that, in the opinion of the Danish Environmental Protection Agency, the content

represents an important contribution to the debate surrounding Danish environmental policy.

While the information provided in this report is believed to be accurate, the Danish Environmental Protection Agency

disclaims any responsibility for possible inaccuracies or omissions and consequences that may flow from them. Neither

the Danish Environmental Protection Agency nor COWI or any individual involved in the preparation of this publication

shall be liable for any injury, loss, damage or prejudice of any kind that may be caused by persons who have acted based

on their understanding of the information contained in this publication.

Sources must be acknowledged.

Survey of n-hexane 3

Contents

Preface ........................................................................................................................... 5

Summary and conclusions ............................................................................................ 8

Sammenfatning og konklusion .....................................................................................12

1. Introduction to the substance .............................................................................. 16 1.1 Definition of the substance ................................................................................................... 16 1.2 Physical and chemical properties ......................................................................................... 17 1.3 Function of the substances for main application areas ....................................................... 17

2. Regulatory framework ......................................................................................... 18 2.1 Legislation ............................................................................................................................. 18

2.1.1 Existing legislation ................................................................................................. 18 2.1.2 Classification and labelling ................................................................................... 22 2.1.3 REACH .................................................................................................................. 23 2.1.4 Other legislation/initiatives .................................................................................. 23

2.2 International agreements .................................................................................................... 23 2.3 Eco-labels ............................................................................................................................. 24 2.4 Summary and conclusions ................................................................................................... 24

3. Manufacture and uses .......................................................................................... 25 3.1 Manufacturing ..................................................................................................................... 25

3.1.1 Manufacturing processes ...................................................................................... 25 3.1.2 Manufacturing sites and volumes ........................................................................ 26

3.2 Import and export n-hexane in Denmark and EU ............................................................. 26 3.3 Use .........................................................................................................................................27

3.3.1 General use .............................................................................................................27 3.3.2 Consumption of n-hexane in EU .......................................................................... 30 3.3.3 Consumption of n-hexane in Denmark ................................................................ 30

3.4 Historical trends in use ........................................................................................................ 33 3.4.1 EU .......................................................................................................................... 33 3.4.2 Denmark ................................................................................................................ 33

3.5 Summary and conclusions ................................................................................................... 34

4. Waste management .............................................................................................. 35 4.1 Waste from manufacture and industrial use of n-hexane ...................................................35 4.2 Waste products from the use of n-hexane in mixtures and articles ...................................35 4.3 Release of n-hexane from waste disposal ............................................................................35 4.4 Summary and conclusions ....................................................................................................35

5. Environmental effects and exposure ................................................................... 36 5.1 Environmental fate .............................................................................................................. 36

5.1.1 Degradation ........................................................................................................... 36 5.1.2 Distribution ........................................................................................................... 36

5.2 Environmental hazard ..........................................................................................................37 5.2.1 Classification ..........................................................................................................37 5.2.2 Environmental effects ............................................................................................37

5.3 Environmental exposure ..................................................................................................... 39


5.3.1 Sources of release .................................................................................................. 39 5.3.2 Monitoring data .................................................................................................... 39

5.4 Environmental impact ......................................................................................................... 40 5.5 Summary and conclusions ................................................................................................... 40

6. Human health effects and exposure..................................................................... 41 6.1 Human health hazard ........................................................................................................... 41

6.1.1 Classification .......................................................................................................... 41 6.1.2 Toxicokinetics......................................................................................................... 41 6.1.3 Acute and chronic effects ...................................................................................... 42 6.1.4 Reproductive toxicity ............................................................................................ 43 6.1.5 Mode of action ....................................................................................................... 44 6.1.6 No effect-levels ...................................................................................................... 44

6.2 Human exposure .................................................................................................................. 46 6.2.1 Direct exposure ..................................................................................................... 46 6.2.2 Indirect exposure ...................................................................................................47

6.3 Bio-monitoring data ............................................................................................................ 48 6.4 Human health impact .......................................................................................................... 49 6.5 Summary and conclusions ................................................................................................... 49

7. Information on alternatives .................................................................................. 51 7.1 Identification of possible alternatives .................................................................................. 51

7.1.1 Alternatives to n-hexane in solvent extraction ..................................................... 51 7.1.2 Alternatives to n-hexane in laboratories .............................................................. 52 7.1.3 Alternatives to n-hexane as a blowing agent.........................................................53 7.1.4 Alternatives to n-hexane as a reaction medium ...................................................53 7.1.5 Alternatives to n-hexane as special purpose solvent and cleaning agent

(degreaser)..............................................................................................................53 7.1.6 Hazard classification of suggested alternatives ....................................................53

7.2 Historical Trends and Future Trends ..................................................................................55 7.3 Summary and Conclusions ...................................................................................................55

8. Abbreviations and acronyms ............................................................................... 56

References ................................................................................................................... 58

Appendix 1: Background information to chapter 2 on legal framework .............. 61


Preface

Background and objectives

The Danish Environmental Protection Agency’s List of Undesirable Substances (LOUS) is intended

as a guide for enterprises. It indicates substances of concern whose use should be reduced or elimi-

nated completely. The first list was published in 1998 and updated versions have been published in

2000, 2004 and 2009. The latest version, LOUS 2009 (Danish EPA, 2011) includes 40 chemical

substances and groups of substances which have been documented as dangerous or which have

been identified as problematic using computer models. For inclusion in the list, substances must

fulfil several specific criteria. Besides the risk of leading to serious and long-term adverse effects on

health or the environment, only substances which are used in an industrial context in large quanti-

ties in Denmark, i.e. over 100 tonnes per year, are included in the list.

Over the period 2012-2015 all 40 substances and substance groups on LOUS will be surveyed. The

surveys include collection of available information on the use and occurrence of the substances,

internationally and in Denmark, information on environmental and health effects, on alternatives

to the substances, on existing regulation, on monitoring and exposure, and information regarding

ongoing activities under REACH, among others.

On the basis of the surveys, the Danish EPA will assess the need for any further information, regula-

tion, substitution/phase out, classification and labelling, improved waste management or increased

dissemination of information.

This survey concerns n-hexane. The substance was included in the first list in 2000 within the

group of simple hydrocarbons and has remained on the list since that time.

Hexane is included because of its problematic health properties, since it has been, amongst others,

been classified as reproduction toxic and damaging to health by prolonged exposure.

The main objective of this study is, as mentioned, to provide background for the Danish EPA’s con-

sideration regarding the need for further risk management measures.

The process

The survey has been undertaken by COWI A/S and Syska Voskian Consulting from September 2013

to June 2014. The work has been followed by an advisory group consisting of:

Peter Hammer Sørensen, Danish EPA, Chemicals

Anne Louise Rønlev, Danish EPA, Aarhus

Nikolai Nilsen, Confederation of Danish Industry

Sonja Hagen Mikkelsen, COWI

Data collection

The survey and review is based on the available literature on the substances, information from da-

tabases and direct inquiries to trade organisations and key market actors.

The data search included (but was not limited to) the following:


Legislation in force from Retsinformation (Danish legal information database) and EUR-Lex

(EU legislation database);

Ongoing regulatory activities under REACH and intentions listed on ECHA’s website (incl.

Registry of Intentions and Community Rolling Action Plan);

Relevant documents regarding International agreements from HELCOM, OSPAR, the Stock-

holm Convention, the PIC Convention, and the Basel Convention.

Data on harmonised classification (CLP) and self-classification from the C&L inventory data-

base on ECHAs website;

Data on ecolabels from the Danish ecolabel secretariat (Nordic Swan and EU Flower) and the

German Angel.

Pre-registered and registered substances from ECHA’s website;

Production and external trade statistics from Eurostat’s databases (Prodcom and Comext);

Export of dangerous substances from the Edexim database;

Data on production, import and export of substances in mixtures from the Danish Product

Register (confidential data, not searched via the Internet);

Date on production, import and export of substances from the Nordic Product Registers as

registered in the SPIN database;

Information from Circa on risk management options (confidential, for internal use only, not

searched via the Internet)

Monitoring data from the National Centre for Environment and Energy (DCE), the Geological

Survey for Denmark and Greenland (GEUS), the Danish Veterinary and Food Administration,

the European Food Safety Authority (EFSA) and the INIRIS database.

Waste statistics from the Danish EPA;

Chemical information from the ICIS database;

Reports, memorandums, etc. from the Danish EPA and other authorities in Denmark;

Reports published at the websites of:

The Nordic Council of Ministers, ECHA, the EU Commission, OECD, IARC, IPCS, WHO,

OSPAR, HELCOM, and the Basel Convention;

Environmental authorities in Norway (Klif), Sweden (KemI and Naturvårsverket), Ger-

many (UBA), UK (DEFRA and Environment Agency), the Netherlands (VROM, RIVM),

Austria (UBA). Information from other EU Member States was retrieved if quoted in

identified literature.

US EPA, Agency for Toxic Substances and Disease Registry (USA) and Environment Can-

ada.

PubMed and Toxnet databases for identification of relevant scientific literature.

Besides, direct enquiries were made to Danish and European trade organisations and a few key

market actors in Denmark.

Background and objectives

The Danish Environmental Protection Agency’s List of Undesirable Substances (LOUS) is intended

as a guide for enterprises. It indicates substances of concern whose use should be reduced or elimi-

nated completely. The first list was published in 1998 and updated versions have been published in

2000, 2004 and 2009. The latest version, LOUS 2009 (Danish EPA, 2011) includes 40 chemical

substances and groups of substances which have been documented as dangerous or which have

been identified as problematic using computer models. For inclusion in the list, substances must

fulfil several specific criteria. Besides the risk of leading to serious and long-term adverse effects on

health or the environment, only substances which are used in an industrial context in large quanti-

ties in Denmark, i.e. over 100 tonnes per year, are included in the list.

Over the period 2012-2015 all 40 substances and substance groups on LOUS will be surveyed. The

surveys include collection of available information on the use and occurrence of the substances,

internationally and in Denmark, information on environmental and health effects, on alternatives


to the substances, on existing regulation, on monitoring and exposure, and information regarding

ongoing activities under REACH, among others.

On the basis of the surveys, the Danish EPA will assess the need for any further regulation, substitu-

tion/phase out, classification and labelling, improved waste management or increased dissemina-

tion of information.


Summary and conclusions

Over the period 2012-2015, all 40 substances and substance groups on the Danish Environmental

Protection Agency’s List of Undesirable Substances (LOUS) will be subject to survey and review. On

the basis of the results, the Danish EPA will assess the need for any further regulation: substitu-

tion/phase out, classification and labelling, improved waste management or increased dissemina-

tion of information.

This survey concerns n-hexane. The substance was included in the LOUS in 1999.

n-Hexane

n-Hexane is a highly volatile hydrocarbon and an ozone precursor. Pure n-hexane occurs in crude

oil in small percentages and can be isolated from a number of oil fractions from the refinery process

(e.g. light and heavy naphtha, light gasoline or BTX (benzene, toluene, and xylene). For example, n-

hexane constitutes about 1 - 3% of unleaded gasoline. The content is less than 0.5 % in synthetic

alkylate gasoline for two- and four stroke engines, sometimes named "environment petrol" accord-

ing to safety data sheets on the Danish market.

Commercial hexane is a mixture that contains approximately 52% n-hexane. Other compounds in

the mixture are e.g. varying amounts of structural isomers and related chemicals, such as

methylpentane and methylcyclopentane.

Regulatory framework

n-Hexane is classified in the following hazard classes: flammable liquids, reproductive toxicity,

aspiration toxicity, specific target organ toxicity after single and repeated exposure, and skin irrita-

tion, and furthermore as hazardous to the aquatic environment.

Hexane is prohibited for use in cosmetic products according to Annex II of the Cosmetic Regulation.

n-hexane is allowed for use as an extraction solvent in production of foodstuffs and food ingredients

with certain restriction regarding residue content and application in preparations of different food

items. n-Hexane is a recognised ozone precursor which is recommended to be included in VOC

measurement programmes according to the Statutory Order on management and control of air

quality. Denmark has adopted the community indicative occupational 8-hour exposure limit value

established for n-Hexane at 20 ppm or 72 mg/m3.

In addition to the legislative instruments that specifically address n-hexane, other instruments are

relevant for n-hexane due to generic classification criteria. The same is the situation in relation to

the EU and the Nordic Eco-labelling schemes.

The substance is currently evaluated under CoRAP (eMSCA; Germany) due to concerns about hu-

man health and wide dispersive use.

Manufacture and uses

The total registered manufacture and import of n-hexane in the EU are indicated to be within the

tonnage band 10,000-100,000 t/y.

In the trade statistics n-hexane is included in broader commodity codes and therefor no specific

data on import/export for n-hexane or for the technical blends of hexanes have been identified.


Due to its technical properties n-hexane is used for a wide variety of products and processes. Except

for its presence in fuels for engines, the major use in Denmark is as an extraction solvent used in

manufacture of vegetable oils, and as a reaction solvent in manufacture of two intermediates in the

production of organophosphorous pesticides. Hexane is recovered and recycled in both production

processes. Manufacture of fish oils is based on a mixture of hexanes. According to information from

the Product Register considerably smaller amounts are used in cleaning and washing agents, adhe-

sives, lubricants, and corrosion inhibitors.

n-Hexane is present in a number of different consumer products such as glues, lubricants, water

proofing sprays, spray paints, car care products, and certain scented products. Concentrations are

typically below 1 % but higher concentrations up to ca. 25 % are seen in products for maintenance

and repair of cars and machinery which may also be used by consumers.

n-Hexane has been the focus for substitution for many decades, but no statistical data have been

identified to illustrate the development.

Waste management

n-Hexane is a highly volatile chemical which will tend to evaporate during production and use. It is

therefore not likely to end up in the waste streams in any considerable amounts.

Environmental effects, fate and exposure

n-Hexane is classified as toxic to aquatic life with long lasting effects (cat. 2).

n-Hexane has a low water solubility (0.0098 g/L) and high vapour pressure (10 kPa). Atmospheric

removal through reaction with hydroxyl radicals might therefore be the most important abiotic

degradation process. By means of a read-across study on biodegradation of naphtha (mainly con-

sisting of C4 - C11 alkanes), hexane was evaluated to be readily biodegradable.

Experimental data on bioaccumulation are not available. However, based on the log P (= log KOW =

3.3 - 4), an estimated log KOC of 2.9 – 3.6, and an estimated BCF of 453, n-hexane is not expected to

bioconcentrate or bioaccumulate significantly in trophic food chains.

Some acute aquatic toxicity data are available, while there is a general lack of chronic and terrestrial

data. The lowest acute toxic effect concentration of n-hexane was determined at 1.5 mg/L in a test

with the small crustacean Artemia salina. However, for all aquatic organisms the reported effect

concentrations cover several orders of magnitude, which is most likely related to methodological

problems and requires very careful interpretation of the listed effect concentrations.

There is considerable potential for releases of n-hexane to environmental media through the use of

fuels for heating or transportation. Atmospheric emissions of n-hexane are due to evaporation dur-

ing processing of the substance or due to incomplete combustion of fuels. Other releases include

industrial discharges, effluents from municipal wastewater treatment plants, and nonpoint-source

runoff, spills, sludge and other waste deposition. Quantitative data on emissions to environmental

compartments in Denmark or Europe could not be identified. Consumer products that contain

small amounts of n-hexane are expected primarily to result in releases to air.

In Denmark, urban background concentrations of n-hexane have been measured in Copenhagen

since 2009, because of the substance’s identification as an ozone precursor. The measurements

have been relatively stable over this period with an average of 0.15 to 0.19 µg/m3.


Human health effects and exposure

n-Hexane is absorbed rapidly through the lungs in experimental animals and is widely distributed

in the body with an affinity for tissues high in lipid content. Particularly high levels have been found

in peripheral nerves. Dermal absorption is limited, but may be enhanced by other solvents. In hu-

mans, n-hexane is absorbed more slowly via the lung and very slowly through the skin.

n-Hexane has low acute toxicity. The critical effects of chronic exposure to n-hexane appear to be

testicular toxicity and neurotoxicity both to the central and peripheral nervous systems. Peripheral

neuropathy is well described after industrial exposure to n-hexane, particularly in shoemakers. The

testicular effects observed in rats have not been well documented in humans.

2,5-Hexanedione is the main metabolite found in humans exposed to n-hexane and the substance

suspected of being responsible for the neurotoxicity of the substance and toxic effects in the testes.

The first symptoms of neurotoxicity are usually sensory and consist of tingling, numbness, burning,

or prickling sensations in the feet or toes followed by progressive muscle weakness first in the lower

and then upper extremities. Distal nerves are more commonly affected.

There is a large number of studies linking occupational exposure to n-hexane to the incidence of

peripheral neuropathy in humans particularly among shoemakers. However, few of these report air

concentrations, and where exposures are quoted it is not clear whether they refer to n-hexane or to

commercial hexane. Also workers were exposed to mixtures of volatile solvents, and the proportions

of n-hexane are not reported.

No information on exposure levels relevant for Danish industrial uses is available. However, the

major applications of the substance as an extraction or reaction solvent take place in closed systems

and are less likely to result in significant workplace exposures.

Very limited data are available regarding consumer exposure in Denmark. As n-hexane is present in

several spray products and taking the volatility of the substance into account, consumers may be

exposed to relatively high concentrations on a short term basis. However, in general the consumers

are not expected to be exposed on frequent basis or for long periods of time, and are thereby not

expected to be at risk in relation to the long-term effects of n-hexane.

Indirect exposure can occur through air, drinking water and food. Urban air concentrations meas-

ured in Copenhagen of on average 0.16-0.19 µg/m3 do not give grounds for major health concerns.

No data on n-hexane in drinking water or food have been identified for the Danish situation. Data

from Canada estimating the total contribution from n-hexane containing food, in particular refined

vegetable oils, do not indicate any risk for the consumer. Based on the limited database, combined

exposures illustrating the Danish situation are not expected to be a concern in relation to the critical

effects of n-hexane.

There is little information on how Danish consumers are exposed to n-hexane and if certain product

types with a high content of n-hexane, e.g. for car repair and maintenance, may result in unaccepta-

ble exposures.

Alternatives to n-hexane

The high volume uses in Denmark are based on n-hexane rich blends of hexane isomers and it does

not seem likely that the n-hexane will be replaced for these applications in the near future. For

solvent extraction of edible oils, only solvents that are allowed according to the legislation in this

area can be used.

Many large companies have developed solvent selection and replacement guides where n-hexane

often is listed as a substance to avoid or restrict where technical requirements makes it possible.


With regard to consumer products, n-hexane has been substituted in many products before the turn

of the millennium and n-hexane is mostly found in smaller concentrations in the majority of the

products. For most types of consumer product alternatives will be available without hexane.

Most of the identified alternatives are also highly flammable and are not safer than n-hexane with

respect to flammability. Heptane, which is often suggested as an alternative has a stronger envi-

ronmental classification and may therefore be a concern in relation to uses such as cleaning and

washing. From a health perspective several of the alternatives share some of the less critical health

effects of n-hexane. Ethanol, which is the least toxic of the alternatives, has been tested as an extrac-

tion solvent, but a technological solution is not available.

Conclusion

The major uses in Denmark of n-hexane as an extraction and reaction solvent occur in closed sys-

tems. Currently it seems that alternative technologies allowing substitution of n-hexane are not fully

developed.

Most releases to the environment will be to air and should be minimised to the extent possible.

Urban ambient air concentrations do not indicate any major health or environmental risk from n-

hexane alone.

With regard to other professional uses information from the Product Register suggest that the con-

sumption has been relatively stable since 2006. It is expected that industry in general has made an

effort to substitute n-hexane containing products already before the turn of the millennium and n-

hexane is often included in purchasing and substitution guidelines from major companies and sec-

tor organisation.

With regard to consumer products no overview of the uses and related exposure situation is availa-

ble. However, available safety data sheets for known product types also intended for the consumer,

suggest the n-hexane concentrations in most products is relatively low. As many of the products are

not used frequently, there is on this basis no indication of a particular consumer risk.

No major data gaps have been identified.


Sammenfatning og konklusion

I perioden 2012-2015 skal alle 40 stoffer og stofgrupper på Miljøstyrelsens liste over uønskede stof-

fer (LOUS) kortlægges og vurderes. På baggrund af resultaterne vil den danske Miljøstyrelsen vur-

dere behovet for yderligere regulering, substitution/udfasning, klassificering og mærkning, forbed-

ret affaldshåndtering eller yderligere informationsaktiviteter.

Denne undersøgelse vedrører n-hexan. Stoffet blev optaget på LOUS i 1999.

n-Hexan

n-Hexan er en flygtig kulbrinte, som medvirker til dannelse af ozon. n-Hexan forekommer i råolie i

små koncentrationer og kan isoleres fra en række oliefraktioner i raffineringsprocessen (fx let og

tung naphtha, let benzin eller BTX (benzen, toluen og xylen). For eksempel udgør n-hexan omkring

1-3% af blyfri benzin, hvorimod indholdet ifølge sikkerhedsdatablade er mindre end 0,5% i syntetisk

alkylatbenzin til to- og fire takts motorer, undertiden kaldet "miljøbenzin".

Kommerciel hexan er en blanding, der indeholder ca. 52% n-hexan. Andre forbindelser i blandingen

er fx varierende mængder af strukturisomere og relaterede kemikalier, såsom methylpentan og

methylcyclopentan.

Lovgivning og anden regulering

n-Hexan er klassificeret som brandfarlig, reproduktionstoksisk, aspirationstoksisk, for specifik

målorgantoksicitet efter enkelt og gentagen eksponering, samt for hudirritation. Derudover er stof-

fet farligt for vandmiljøet.

Hexan er forbudt til anvendelse i kosmetiske produkter i henhold til bilag II i kosmetikforordnin-

gen. n-Hexan er tilladt til brug som et ekstraktionsmiddel ved fremstilling af levnedsmidler og lev-

nedsmiddelingredienser med visse begrænsninger med hensyn til restindhold og anvendelse i frem-

stillingen af forskellige fødevarer. n-Hexan er en anerkendt ozondanner, som anbefales at indgå i

VOC måleprogrammer i henhold til bekendtgørelsen om styring og kontrol af luftkvaliteten. Dan-

mark har adopteret EUs indikative 8-timers grænseværdi for eksponering i arbejdsmiljøet på 20

ppm eller 72 mg/m3.

Ud over den lovgivning, der specifikt nævner n-hexan, er n-hexan også omfattet af anden lovgiv-

ning, der omfatter stoffer på baggrund af generiske klassifikationskriterier. Det samme er tilfældet i

forhold til EUs og den Nordiske miljømærkeordning.

Stoffet er i øjeblikket under evaluering i CoRAP (eMSCA; Tyskland) grund af bekymringer for

menneskers sundhed og udbredt åben anvendelse.

Fremstilling og anvendelse

Den samlede registrerede fremstilling og import af n-hexan i EU angives at være inden for mængde-

intervallet 1.000-10.000 t/år.

I handelsstatistikken er n-hexan inkluderet i bredere varekoder og der er derfor ingen specifikke

oplysninger om import/eksport af stoffet, eller af de tekniske blandinger af hexan, som er identifi-

ceret.


På grund af stoffets tekniske egenskaber anvendes n-hexan til en bred vifte af produkter og proces-

ser. Bortset fra forekomsten i brændstoffer til motorer er den væsentligste anvendelse i Danmark

som ekstraktionsmiddel ved fremstilling af vegetabilske olier og som opløsningsmiddel ved frem-

stilling af pesticider. Hexan genindvindes og genbruges i begge produktionsprocesser. Fremstilling

af fiskeolier er baseret på en blanding af hexaner. Ifølge oplysninger fra Produktregisteret anvendes

mindre mængder i rengørings-og vaskemidler, lime, smøremidler og i korrosionsinhibitorer.

n-Hexan findes i en række forskellige forbrugerprodukter såsom lim, smøremidler, imprægnerings-

sprays, sprøjtemaling, bilplejeprodukter og visse parfumerede produkter. Koncentrationen er typisk

under 1 %, men højere koncentrationer på op til ca. 25% er set i produkter til eksempelvis vedlige-

holdelse og reparation af biler og maskiner. Disse produkter kan også anvendes af forbrugere.

n-Hexan har været fokus for substitution i mange årtier, men der er ikke ingen identificeret statisti-

ske data til illustration af udviklingen.

Affaldshåndtering

n-Hexan er et letflygtigt kemikalie, som vil have en tendens til at fordampe under produktion og

anvendelse. Det er derfor ikke sandsynligt, at stoffet ender i affaldsstrømmene i nogen betydelig

mængde.

Miljømæssige effekter, skæbne og eksponering

n-Hexan er klassificeret som giftigt for vandlevende organismer, med langvarige virkninger (Kat. 2).

n-Hexan har lav opløselighed i vand (0,0098 g/l) og højt damptryk (10 kPa). Atmosfærisk fjernelse

gennem reaktion med hydroxylradikaler er sandsynligvis den vigtigste abiotiske nedbrydningsvej

for stoffet i miljøet. Baseret på "read-across" fra en undersøgelse om biologisk nedbrydning af nafta

(hovedsageligt bestående af C4 - C11 alkaner), er hexan vurderet at være let bionedbrydelig.

Eksperimentelle data om bioakkumulering er ikke tilgængelige. Men baseret på logP (= log KOW =

3,3 - 4) , en estimeret log Koc på 2,9-3,6 og en anslået BCF på 453 , forventes n- hexan ikke at bio-

koncentrere eller bioakkumulere væsentligt i trofiske fødekæder.

Visse data for akut toksicitet i vandmiljøet er til rådighed, mens der er en generel mangel på kroni-

ske data samt terrestriske data generelt. Den laveste koncentration med akut giftvirkning af n -

hexan blev bestemt til 1,5 mg/L i en test med krebsdyret Artemia salina. Men for alle vandorganis-

mer dækker de rapporterede effektkoncentrationer flere størrelsesordener, hvilket sandsynligvis

skyldes metodologiske problemer ved de udførte test. Der er derfor behov for meget omhyggelig

fortolkning af de rapporterede effektkoncentrationer.

Der er et betydeligt potentiale for udslip af n-hexan til luftmiljøet som resultat af anvendelse af

brændstoffer til opvarmning eller transport. Atmosfæriske emissioner af n-hexan skyldes fordamp-

ning ved de industrielle anvendelser af stoffet eller på grund af ufuldstændig forbrænding af brænd-

stoffer. Andre afgivelser omfatter industrielle udledninger, spildevand fra kommunale renseanlæg

og diffus overfladeafstrømning, spild samt deponering af slam og andet affald. Der er ikke identifi-

ceret kvantitative data om emissioner til m i Danmark eller Europa. Forbrugerprodukter, der inde-

holder små mængder af n-hexan, forventes primært at give anledning til afgivelse til luft.

I Danmark er baggrundskoncentrationer af n-hexan i bymiljøer blevet målt i København siden

2009, på grund af, at stoffet er identificeret som en precursor for ozon. Niveauerne har ligget rela-

tivt stabilt i denne periode med en gennemsnitskoncentration på 0,15-0,19 μg/m3.


Sundhedseffekter og eksponering

n-Hexan absorberes hurtigt gennem lungerne i forsøgsdyr og distribueres i kroppen med en affini-

tet for væv med højt fedtindhold. Særligt høje niveauer er blevet fundet i de perifere nerver. Dermal

absorption er begrænset, men kan øges af andre opløsningsmidler. Hos mennesker optages n-hexan

langsommere via lungerne end i dyr og meget langsomt gennem huden.

n-Hexan har lav akut toksicitet. De kritiske effekter af kronisk eksponering for n-hexan synes at

være testikeltoksicitet og neurotoksicitet i forbindelse med både det centrale og perifere nervesy-

stem. Perifer neuropati er velbeskrevet i forbindelse med industriel eksponering for n-hexan, især

blandt arbejdere i skoindustrien. Effekterne som ses på testikler hos rotter er ikke vel-dokumenteret

hos mennesker.

2,5-Hexandion er den vigtigste metabolit hos mennesker, der har været udsat for n-hexan, og stoffet

mistænkes for at være årsagen til neurotoksicitet og toksiske effekter i testiklerne. De første symp-

tomer på neurotoksicitet er normalt sensoriske og består af prikken, følelsesløshed, brændende eller

prikkende fornemmelser i fødder eller tæer efterfulgt af progressiv muskelsvækkelse først i de ne-

derste og derefter de øvre ekstremiteter. Distale nerver påvirkes normalt mere.

Der er et stort antal undersøgelser, der forbinder erhvervsmæssig eksponering for n-hexan med

forekomsten af perifer neuropati hos mennesker især blandt skoarbejdere. Imidlertid rapporterer få

af disse undersøgelser om luftkoncentrationen, og i de tilfælde, hvor eksponeringen er nævnt, er det

ikke klart, om der henvises til n-hexan eller kommercielt hexan. Det rapporteres heller ikke om

arbejdere blev udsat for blandinger af flygtige opløsningsmidler, og i givet fald hvad andelen af n-

hexan var.

Der er ikke fundet oplysninger om eksponeringsniveauer relevante for danske anvendelser i indu-

strien. De væsentligste anvendelser af stoffet som ekstraktions- eller reaktions-opløsningsmiddel

finder sted i lukkede systemer og medfører næppe væsentlige eksponeringer i arbejdsmiljøet.

Der er begrænsede data tilgængelige vedrørende forbrugernes eksponering i Danmark. Da n-hexan

er til stede i flere sprayprodukter og stoffet er flygtigt, kan forbrugerne potentielt udsættes for rela-

tivt høje koncentrationer i kort tid. Generelt forventes forbrugerne dog ikke at blive eksponeret

hverken hyppigt eller i længerevarende perioder, og dermed forventes der ikke at være nogen væ-

sentlig fare forhold til de langsigtede effekter af n-hexan.

Indirekte eksponering kan forekomme gennem luft, drikkevand og fødevarer. Koncentrationer på

gennemsnitligt 0,16-0,19 μg/m3 målt i byluften i København giver ikke anledning til væsentlige

sundhedsmæssige betænkeligheder. Der er ikke fundet data om n-hexan i drikkevand eller fødeva-

rer, som kan anvendes til at beskrive situationen I Danmark. Estimater fra Canada over det samlede

bidrag af n-hexan med mad, især raffinerede vegetabilske olier, indikerer ikke nogen risiko for for-

brugeren. Baseret på de begrænsede data, der er til rådighed, antages kombineret eksponering, ikke

at ville udgøre et problem i forhold til de kritiske effekter af n-hexan.

Der er ikke meget information om danske forbrugeres udsættelse for n-hexan, og om hvorvidt visse

produkttyper med højt indhold af n-hexan til fx bilreparation og vedligeholdelse kan resultere i

uacceptable eksponeringer.

Alternativer til n-hexan

Det store forbrug af n-hexan i Danmark er baseret på n-hexan-rige blandinger af hexanisomerer, og

det synes ikke sandsynligt, at n-hexan vil blive erstattet til disse anvendelser i den nærmeste frem-

tid. Til udvinding af spiseolier kan der kun anvendes opløsningsmidler, der er tilladt i henhold til

lovgivningen.


Mange store virksomheder har udviklet retningslinjer for indkøb og substitution af opløsningsmid-

ler, hvor n -hexan ofte er opført som et stof, der skal undgås eller begrænses, hvis tekniske krav gør

det muligt.

Med hensyn til forbrugerprodukter, er n-hexan blevet erstattet i mange produkter før årtusindskif-

tet og n-hexan findes for det meste i mindre koncentrationer i produkterne. For de fleste typer af

forbrugerprodukter vil der være tilgængelige alternativer uden hexan.

Hovedparten af de identificerede alternativer er også klassificerede som brandfarlige og er dermed

ikke sikrere end n-hexan med hensyn til brandfarlighed. Heptan, der ofte foreslås som et alternati-

ve, har en strengere miljøfareklassificering og kan derfor være et problem i forhold til nogle anven-

delser såsom rengøring. Fra et sundhedsmæssigt perspektiv deler flere af alternativerne nogle af de

mindre kritiske sundhedsmæssige effekter med n-hexan. Ethanol, som er det mindst toksiske af de

nævnte alternativer, er blevet testet som ekstraktionsmiddel, men en teknologisk løsning er ikke

tilgængelig.

Konklusion

De vigtigste anvendelser af n-hexan i Danmark er som ekstraktions- og reaktionsopløsningsmiddel i

lukkede systemer. I øjeblikket er lader det ikke til, at alternative teknologier er tilstrækkeligt udvik-

let med henblik på substitution af n-hexan.

De fleste udledninger til miljøet vil være til luft og bør minimeres i det omfang, det er muligt. Kon-

centrationer i byluften indikerer ikke umiddelbart nogen væsentlig sundheds-eller miljørisiko fra n-

hexan alene.

Med hensyn til andre erhvervsmæssige anvendelser tyder oplysninger fra Produktregisteret på, at

forbruget har været relativt stabilt siden 2006. Det antages, at industrien generelt har gjort en ind-

sats for at erstatte produkter med indhold af n-hexan allerede før årtusindskiftet, og n- hexan ind-

går fortsat ofte i indkøbs-og substitutionsvejledninger fra store virksomheder og brancheorganisati-

oner.

Med hensyn til forbrugerprodukter er der på nuværende tidspunkt ikke noget overblik over anven-

delser og eksponeringssituationer forbundet med brug af n-hexan. Sikkerhedsdatablade for kendte

produkttyper, som også er beregnet til forbrugerne, tyder på, at koncentrationerne af n-hexan i de

fleste produkter er forholdsvis lave. Da mange af disse produkter, ikke anvendes hyppigt, er der på

det foreliggende grundlag ingen indikation af en væsentlig risiko for forbrugerne.

Der er ikke identificeret væsentlige datamangler.


1. Introduction to the sub-stance

1.1 Definition of the substance

The name and other identifiers of n-hexane included in this study are listed in Table 1.

TABLE 1

NAME AND OTHER IDENTIFIERS OF N-HEXANE

Substance name n-hexane

EC number 203-777-6

CAS number 110-54-3

Synonyms hexane; normal hexane; hexyl hydride; skellysolve B;

dipropyl; gettysolve-b; hex

Molecular formula C6H14

Structure

Molecular weight 86.18 g/mol

n-Hexane is a straight-chain, fully saturated hydrocarbon with six carbon atoms.

Pure n-hexane occurs in crude oil in small percentages and can be isolated from a number of oil

fractions from the refinery process (e.g. light and heavy naphtha, light gasoline or BTX (benzene,

toluene, and xylene). For example, n-hexane constitutes about 1 - 3% of unleaded gasoline (ASTDR,

1999) and less than 0.5 % in synthetic alkylate gasoline for two- and four stroke engines, sometimes

named "environment petrol" according to safety data sheets on the Danish market. Special know-

how and technology is required for the production of high-purity n-hexane.

Commercial hexane is a mixture that contains approximately 52% n-hexane (US EPA, 2005). Other

compounds in the mixture are e.g. varying amounts of structural isomers and related chemicals,

such as methylpentane and methylcyclopentane.

n-Hexane is a major component of some of fractions from distillation of crude oil. A large number

of CAS numbers exist for these “Substances of Unknown or Variable composition” (UVCB). Until

now, there has not been a coordinated use of the CAS numbers for mixtures containing a certain

amount of n-hexane, a scan of Safety Data Sheets on the internet confirms this confusion. The Hy-

drocarbon Solvents REACH consortium undertaking the collective activities related to the registra-

tion of Hydrocarbon Solvents under REACH, has developed a naming convention for hydrocarbon

solvents based on the chemical composition of the substance (HSPA, 2011). The new substance

definitions and a category approach for the toxicological assessments are the basis for the classifica-

http://www.reachcentrum.eu/Consortia%20Documents/P-I163/Other/P-I163_HSPA_Naming_convention_2011.03.pdf


tion and labelling of those substances. The hydrocarbon solvents described by a HSPA substance

are a specific and narrower defined subset of one or more existing CAS numbers. However, this

survey focuses on the substance n-hexane with the CAS no. 110-54-3. Further information on mix-

tures containing n-hexane is provided in chapter 3.

1.2 Physical and chemical properties

n-Hexane is a highly volatile hydrocarbon. The physical and chemical properties of n-hexane are

shown in Table 2. The listed properties mainly refer to the registration dossiers available at ECHA's

website. The registration dossiers may include different values for the same parameter; in this case,

all values are indicated. TABLE 2

PHYSICAL AND CHEMICAL PROPOERTIES OF THE SUBSTANCE (ECHA 2013).

Property n-hexane

Physical state Liquid

Melting point -95.35 °C

Boiling point 68.73 °C

Relative density 0.6606 g/cm³

Vapour pressure 10 kPa @ 9.8°C (16.2 kPa @ 20°C1)

Surface tension 17.89 mN/m @ 25°C

Water solubility (mg/L) 0.0098 g/L @ 25°C

Log P (octanol/water) 4

1.3 Function of the substances for main application areas

Highly purified n-hexane is primarily used as a reagent or solvent for laboratory applications.

Commercial hexane is an important solvent in many industries. In the food industry, mixtures con-

taining n-hexane are used in processes for the extraction of edible fats and oils. n-Hexane is the

solvent base for many commercial products, such as glues, inks, cements, paint thinners, cleaning

agents and degreasers. It is also a component in fuels, and used as a blowing agent in polyurethane

production.

1 http://Calculation of vapour pressure at 20°C: ddbonline.ddbst.com/AntoineCalculation/AntoineCalculationCGI.exe

http://calculation/


2. Regulatory framework

This chapter gives an overview of how n-hexane is addressed in existing and upcoming EU and

Danish legislation, international agreements and by EU and Nordic eco-label criteria. The chapter

primarily focuses on legislation where n-hexane is addressed specifically by chemical name or CAS

number. Legislation, where the substance is implicitly addressed, i.e. where n-hexane is included in

the overall scope of a regulation/directive (e.g. due to the substance classification), is not listed.

Examples of such legislation is the Statutory order on VOCs2 implementing the EU Directive on

Industrial emissions and the Statutory order on major accident hazards3 implementing the Seveso

Directive. These are of course equally important in relation to n-hexane.

In Appendix 1, a brief overview of legal instruments in the EU and DK is presented. The appendix

gives a brief introduction to chemicals legislation, explains the lists referred to in section 2.1.3 on

Registration, Evaluation, Authorisation and Restriction of Chemicals (REACH), and provides a brief

introduction to international agreements and the EU and Nordic ecolabelling schemes.

2.1 Legislation

This section will first list existing legislation addressing n-hexane, and then give an overview of on-

going activities, focusing on where n-hexane is mentioned in the pipeline in relation to various

REACH provisions.

2.1.1 Existing legislation

Table 3 provides an overview of existing key legislation addressing n-hexane. For each area of legis-

lation, the table first lists the EU legislation (if applicable) and then (as concerns directives) existing

transposition into Danish law and/or other national rules. The latter will only be elaborated upon in

case of Danish rules differ from EU rules.

By European legislation, hexane is prohibited in cosmetic products through the Cosmetics regula-

tion. The Directive 2009/32/EC on extraction solvents used in the production of foodstuffs indi-

cates application areas as well as maximum residues of hexane in certain foodstuffs where hexane

extraction is used. The residue limit values are implemented in Denmark by the Statutory Order on

Additives in Food.

The Commission directive on indicative occupational exposure values sets out an 8-hour limit value

of 72 mg/m³ (20 ppm) for hexane. The Danish occupational limit value is congruent with the EC

indicative limit values. Short-term exposure limit values have not been defined for hexane in nei-

ther Danish nor European legislation. However, the exposure limits defined in the Executive Order

no. 507 of 17th May 2011 indicate that the short-time exposure limit never must exceed the 2-times

exposure limit value when exposed over 15 min.

2 Bekendtgørelse nr. 1452 af 20/12/2012 om anlæg og aktiviteter, hvor der bruges organiske opløsningsmidler 3 Bekendtgørelse nr. 1666 af 14/12/2006 om kontrol med risikoen for større uheld med farlige stoffer


TABLE 3

LEGISLATION ADRESSING N-HEXANE

Legal instrument*1 EU/

DK

Substance as

specified by

the instru-

ment

Requirements

Legislation addressing substances

Regulation (EC) No

1272/2008 of the European

Parliament and of the Council of

16 December 2008 on classifica-

tion, labelling and packaging of

substances and mixtures, amend-

ing and repealing Directives

67/548/EEC and 1999/45/EC

EU n-hexane, 203-

777-6, 110-54-3

n-Hexane is included in the List of har-

monised classifications of hazardous

substances

Legislation addressing products

Regulation (EC) No

1223/2009 of the European

Parliament and of the Council of

30 November 2009 on cosmetic

products

EU Hexane, 110-54-3 Listed in ANNEX II: LIST OF SUB-

STANCES PROHIBITED IN COSMETIC

PRODUCTS

Directive 2009/32/EC of the

European Parliament and of the

Council of 23 April 2009 on the

approximation of the laws of the

Member States on extraction

solvents used in the production of

foodstuffs and food ingredients

EU Hexane4 Hexane is listed in ANNEX I including

extraction solvents which are allowed in

food or raw material processing.

The following use conditions (with maxi-

mum residues in the extracted food stuff)

have been defined for hexane:

- Production or fractionation of fats and

oils and production of cocoa butter (1

mg/kg)

- Preparation of defatted protein products

and defatted flours (10 mg/kg in the food

containing the defatted protein products

and the defatted flours, 30 mg/kg in the

defatted soya products as sold to the final

consumer)

- Preparation of defatted cereal germs

(5 mg/kg)

The maximum residue limit in the food-

stuff due to the use of hexane in the prep-

aration of flavourings from natural fla-

4 Hexane means a commercial product consisting essentially of acyclic saturated hydrocarbons containing six

carbon atoms and distilling between 64 °C and 70 °C



DK

Substance as

specified by

the instru-

ment

Requirements

vouring materials is 1 mg/kg.

The combined use of hexane and ethylme-

thylketone for extraction is forbidden.

Statutory Order No 542 of

27/05/2013 on additives, etc. to

foods

[Bekendtgørelse om tilsætninger

mv. til fødevarer, BEK no. 542,

27/05/2013],

Ministry of Food, Agriculture and

Fisheries of Denmark

DK Hexane Included in part II and part III describ-

ing extraction agents’ allowed application

areas and maximum residues in foods

The maximum residues for the specified

application areas are congruent with

Directive 2009/32/EC

Legislation addressing emissions to the environment (Ministry of Environment)

Statutory Order No 1326 of

21/12/2011 on assessment and

management of air quality

[Bekendtgørelse om vurdering og

styring af luftkvaliteten, BEK nr.

1326 af 21/12/2011]

Ministry of Environment

DK n-Hexane The Danish EPA divides the country into

zones and agglomerations, in which the

air quality is to be assessed and managed

in accordance with Directive 2008/50/EC

and Directive 2004/107/EC.

n-Hexane is listed in appendix X Meas-

urements of ozone precursors:

n-hexane is included in the list of recom-

mended measured VOC.

Legislation addressing occupational exposures (Ministry of Employment)

Commission Directive

2006/15/EC of 7 February

2006 establishing a second

list of indicative occupational

exposure limit values in im-

plementation of Council Di-

rective no 98/24/EC amend-

ing Directives 91/322/EEC

and 2000/39/EC

EU 110-54-3,

n-hexane

Listed in the Annex on INDICATIVE

OCCUPATIONAL EXPOSURE LIMIT

VALUES.

Limit values are

8 hours: 72 mg/m³ (20 ppm).

There are no short-term limit values or

annotations for hexane.

Executive Order no. 507 of

17/05/2011 on Limit Values

for Substances and Materials

[Bekendtgørelse om grænseværdi-

er for stoffer og materialer, BEK

nr. 507 af 17/05/2011]

DK n-Hexane The order addresses any work with sub-

stances and materials, and any risk of

exposure to workplace substances and

materials.

Hexane is listed in Section A on limit

values for air pollution - List of limit

values for gases, vapours and particulate



DK

Substance as

specified by

the instru-

ment

Requirements

pollution.

Limit values are congruent with the EF

indicative limit values.

Executive Order No. 301 of

13/05/1993 on Determination

of Code Numbers,

[Bekendtgørelse om fastsættelse af

kodenumre, BEK nr 301 af

13/05/1993] /Danish Ministry of

Employment

Executive Order No. 302 of

13.05.1993 on Work with

Code-Numbered Products

[Bekendtgørelse om arbejde med

kodenummererede produkter,

BEK nr. 301 af 13/05/1993]

/Danish Ministry of Employment

Executive Order on Working

with Substances and Materi-

als.

[Arbejdstilsynets bekendtgørelse

nr.292 af 26. April 2001 med

senere ændringer.]

Bekendtgørelse om arbejdets

udførelse nr. 559 af 17. juni 2004.

DK n-Hexane

The Metrological Occupational Air Re-

quirements, called MAL [Danish:

Måleteknisk Arbejdshygiejnisk Luftbehov]

are defined for n-hexane as follows:

n-Hexane content > 0%

- MAL-factor (m³ air / 10 g substance):

78

- Content (limit weight %) / number

after the hyphen: ≥ 0% / -1

Defines minimum safety measures which

have to be applied when working with

code-numbered products depending on

working situations (outside, inside, large

or small application areas) and processes

(e.g. painting, grouting).

The executive order implements the EU

Directive No 98/24/EC on the protection

of the health and safety of workers from

the risks related to chemical agents at

work. According to the Statutory order the

employer has the obligation to:

- plan the work, in order to reduce any

risk to the safety and health of workers

rising from the presence of hazardous

chemical agents,

- replace hazardous substances, materials

and work processes by less hazardous

substances, materials and work processes,

and

- develop workplace guidelines for the use

of hazardous substances and materials.

Section 16. Any unnecessary exposure of

substances and materials must be avoid-

ed.

*1 Unofficial translation of name of Danish legal instruments.


2.1.2 Classification and labelling

Harmonised classification in the EU

Table 4 lists the harmonised classification and labelling for n-hexane according to Annex VI of the

CLP Regulation. n-Hexane is classified in the following hazard classes: flammable liquids, repro-

ductive toxicity, aspiration toxicity, specific target organ toxicity after single and repeated exposure,

and skin irritation, and furthermore as hazardous to the aquatic environment.

TABLE 4

HARMONISED CLASSIFICATION ACOORDING TO ANNEX VI OF REGULATION (EC) NO 1272/2008 (CLP REGULATION)

Index No International

chemical iden-

tification

CAS No Classification Labelling

Hazard

Class and

Category

Code(s)1

Hazard

statement

Code(s)2

Pictogram

601-037-00-0 n-hexane 110-54-3 Flam. Liq 2 H225

Skin Irrit. 2 H315

Asp. Tox. 1 H304

STOT SE 3 H336

STOT RE 2 3 H373 4

Repr. 2 H361f 5

Aquatic

Chronic 2

H411

1 Hazard Class - Flam. Liq.: Flammable liquid; Skin Irrit.: Skin irritation; STOT SE: Asp. Tox.: Aspiration

toxicity; Specific target organ toxicity — single exposure; STOT RE: Specific target organ toxicity — re-

peated exposure; Repr.: Reproductive toxicity; Aquatic Chronic: Hazardous to the aquatic environment.

2 Hazard statement codes - H225: Highly flammable liquid and vapour; H315: Causes skin irritation; H304:

May be fatal if swallowed and enters airways; H336: May cause drowsiness or dizziness; H373: May cause

damage to organs through prolonged or repeated exposure; H361f: Suspected of damaging fertility; H411:

Toxic to aquatic life with long lasting effects.

3 Minimum classification, applies when classification according to the criteria in Directive 67/548/EEC

does not correspond directly to the classification in a hazard class and category under the CLP Regulation.

4 Hazard statement not specifying the route of exposure as the necessary information is not available.


5 ‘Suspected of damaging fertility or the unborn child’. According to the criteria, the general hazard state-

ment can be replaced by the hazard statement indicating only the property of concern, where either fertili-

ty or developmental effects are proven to be not relevant.

Self-classification in the EU

The notified classifications are almost all completely congruent with the harmonised classification.

A few notifiers do report acute toxicity H331 (3 notifiers out of ca. 2000) and STOT RE 1; H372

instead of H373 (17 notifiers out of ca. 2000).

2.1.3 REACH

n-Hexane is not restricted in the REACH regulation (Regulation (EC) No 1907/2006 of the Europe-

an Parliament and of the Council of 18 December 2006 concerning the Registration, Evaluation,

Authorisation and Restriction of Chemicals).

n-Hexane is registered with a full registration under REACH in the 10,000 - 100,000 t/y band.

Candidate list / Authorisation List / REACH Annex XIV

n-Hexane is not on the Candidate list of Substances of Very High Concern for Authorisation, or on

the Authorisation list. The substance is not included in REACH Annex XIV (List of substances sub-

ject to authorisation).

Registry of Intentions

n-Hexane is listed in the registry of withdrawn Harmonised Classification and Labelling intentions

and submissions. The intention was originally submitted by Norway who has earlier had a different

classification of n-hexane than the EU.

Substance evaluation

n-Hexane is included in the first Community Rolling Action Plan (CoRAP 2012-2014) for evaluation

in the year 2012 by Germany due to concerns about human health. N-hexane was selected for sub-

stance evaluation due to the CMR-properties and neurotoxic effects. There are several registrations

of different registrants leading to a higher tonnage and exposure level than concluded in the single

dossiers. The intention of the substance evaluation is to evaluate the risks arising from the aggre-

gated exposure. The current status is marked as “ongoing” (May 2014).

TABLE 5

SUBSTANCES IN THE DRAFT COMMUNITY ROLLING ACTION PLAN, 2012-2014 (ECHA, 2014).

CAS No EC No Substance

Name

Year Member

State

Initial grounds for concern

110-54-3 203-777-6 n-hexane 2012 Germany Human health/CMR and neurotoxicity;

Exposure/Wide dispersive use, high

aggregated tonnage

2.1.4 Other legislation/initiatives

No other legislation or initiatives have been identified.

2.2 International agreements

n-Hexane is not mentioned in the international conventions and agreements that are relevant for

this survey (OSPAR, HELCOM, ROTTERDAM, STOCKHOLM, Basel, CLRTAP). These conventions

are concerned with environmental effects of chemical substances and/or persistent substances,

properties which are not the main concerns relating to n-hexane.

For further information on the conventions, consult Appendix 1:


2.3 Eco-labels

The EU and Nordic eco-labelling have been searched for criteria excluding or restricting the use of

n-hexane in eco-labelled products. n-Hexane is not mentioned specifically in any of the relevant

criteria. It should however be stressed that n-hexane may be restricted due to general restrictions

based on classification of substances as e.g. STOT RE or Repr. or according to criteria related to

VOC content. For example, ingredients classified as dangerous substances, such as substances with

risk phrases R62 (Possible risk of impaired fertility) are not allowed in eco-labelled indoor paints

and varnishes (Nordic Ecolabelling, 2014a; n-hexane is classified as R62 according to the DSD Clas-

sification). (The criteria document for indoor paints and varnishes is currently under revision).

The same applies to e.g. product groups of car and boat care products (Nordic Ecolabelling, 2014b),

chemical building products (Nordic Ecolabelling, 2014c), and office and hobby supplies (Nordic

Ecolabelling, 2014d), in which hexane could be present as a constituent (solvent) or as a residue

from use as a process chemical.

2.4 Summary and conclusions

n-Hexane is classified in the following hazard classes: flammable liquids, reproductive toxicity,

aspiration toxicity, specific target organ toxicity after single and repeated exposure, and skin irrita-

tion, and furthermore as hazardous to the aquatic environment.

Hexane is addressed in several Danish and European legislative instruments. Hexane is prohibited

for use in cosmetic products according to Annex II of the Cosmetic Regulation. Residue content and

application in preparations of different food items is defined by Danish legislation.

With respect to the environment, hexane is recommended to be measured in assessing and manag-

ing air quality, since it is recognized as an ozone precursor VOC.

A community indicative occupational exposure limit value is established for n-hexane. The Danish

occupational exposure limit is identical with the European indicative 8-hour limit at 20 ppm.

The substance is currently evaluated under CoRAP due to concerns about human health and wide

dispersive use.


3. Manufacture and uses

3.1 Manufacturing

3.1.1 Manufacturing processes

Light naphtha is refined to obtain pure n-hexane (REACH registration number 01-211-948-0412-

44-xxxx).


fractions from the refinery process (e.g. light and heavy naphtha, light gasoline or BTX (benzene,

toluene, and xylene). It is difficult to achieve high purity of n-hexane and special know-how and

technology is required. The processes involve molecular sieve adsorption (where the straight n-

paraffin is held in the cavities of the sieve and branched hydrocarbons go straight through), batch

azeotropic distillation, superfractionation and extractive distillation (Environment Canada, 2009).

The energy consumption for n-hexane purification using the mentioned traditional purification

technologies is high.

In addition to pure n-hexane, a number of C6 rich aliphatic naphthas with a content of n-hexane

have been registered under REACH and are sold under different names and CAS numbers. The

following table from the Hydrocarbon Solvents Producers Association, HSPA, shows the different

C6 products that have been defined by HSPA for REACH registration (Table 6). These broader

range distillation point substances are manufactured via distillation of a suitable hydrocarbon feed-

stock, which may be straight-run gasoline distilled from crude oil. Note that the CAS numbers pro-

vided in the table are used to define C6 aliphatics as well as other aliphatics.

Hi TABLE 6

DIFFERENT C6 PRODUCTS ACCORDING TO THE HYDROCARBON SOLVENTS PRODUCERS ASSOCIATION (HSPA, 2011)

HSPA Cate-

gory

HSPA substance

name

REACH

registra-

tion pro-

visional

EC No.

Related

CAS

No.(s)

Related CAS No.(s)

Substance name

C6 Aliphatics Normal-Hexane 203-777-6 92112-69-1

Hexane,-branched-and-

linear

110-54-3 Hexane

C6 Aliphatics

Hydrocarbons, C6,

isoalkanes, <5%

n-hexane

931-254-9 64742-49-0

Naphtha (petroleum),

hydrotreated

light

C6 Aliphatics

Hydrocarbons, C6,

n-alkanes,

isoalkanes, cyclics,

n-hexane rich

925-292-5

64742-49-0 Naphtha (petroleum),

hydrotreated light

93165-19-6 Distillates (petroleum),

C6-rich

92112-69-1 Hexane,-branched-and-

linear


HSPA Cate-

gory

HSPA substance

name

REACH

registra-

tion pro-

visional

EC No.

Related

CAS

No.(s)

Related CAS No.(s)

Substance name

C6 Aliphatics C6 Aliphatics 930-397-4

92062-15-2

Solvent naphtha (petrole-

um),

hydrotreated light naph-

thenic

64742-49-0

Naphtha (petroleum),

hydrotreated

light

C6 Aliphatics

Hydrocarbons, C7,

n-alkanes,

isoalkanes, cyclics

927-510-4 64771-72-8 Paraffins (petroleum),

normal C5-20

3.1.2 Manufacturing sites and volumes

Based on information in the REACH registration and Internet search, no manufacturing site of n-

hexane has been identified in Denmark.

Compared with the number of European manufacturers of commercial hexane, there are few manu-

facturers of pure n-hexane. The following companies and sites in Europe have registered n-hexane

under REACH and are manufacturing in Europe:

Bitolea S.p.A, Italy: n-hexane 95 and n-hexane 99;

DHC Solvent Chemie GmBH, Germany: n-hexane 95 and n-hexane 99;

Haltermann GmbH: n-hexane 95 and n-hexane 99;

Neste Oil Oyj, Finland. It has been confirmed by Neste Oil that n-hexane is an isolated inter-

mediate in the petroleum refinery, not a product.

There are no statistical data to support an estimate of the volume manufactured by company or the

total volume manufactured in Europe. The REACH registration is in the 10,000 – 100,000 tonnes

per annum range (aggregated tonnage) but includes also volumes from importers that have regis-

tered.

3.2 Import and export n-hexane in Denmark and EU

In the recent nomenclature, n-hexane is not included (Commission Regulation (EU) No 927/2012)

as a special entry, but covered by the generic CN code 2901 10 00 (Acyclic hydrocarbons – saturat-

ed). It has therefore not been possible to identify import and export data for n-hexane for neither

Denmark nor the EU. Likewise, there is no PRODCOM code available for n-hexane.

Some companies have registered n-hexane under REACH but do not seem to be manufacturing in

Europe (registration as only representatives):

Chevron Philips Chemicals International NV, Belgium. High purity hydrocarbons and solvents

are produced by Chevron Philips Chemicals only in Texas (information from their web site)

The following only representative companies have registered n-hexane under REACH for import by

their clients:

BiPRO GmbH Grauertstrasse 12, 81545, Munich, Germany

REACHLaw Ltd. Keilaranta 15, 02150, Espoo, Finland


3.3 Use

3.3.1 General use

n-Hexane’s high solubility for oil combined with its low boiling point makes it suitable for the use in

a wide variety of applications. The major global uses of n-hexane as reported in the literature are

listed below (Environment Canada, 2009; US EPA, 2005):

a component in fuels and other petroleum products

solvent extraction of vegetable oils and defatting of fish meal (extraction of fish oil)as blowing

agent

as an inert solvent for carrying out other chemical reactions (“reaction solvent” “reaction me-

dium” or “diluent”)

special purpose solvent and cleaning agent (degreaser)

in laboratories

Detailed information about the global or EU consumption of n-hexane for different uses has not

been possible to obtain.

Component in fuels and other petroleum products:

Motor fuel contains small amounts (1-3%) of n-hexane. End-use fuels formulated with n-hexane

containing products is a major global use of n-hexane. This use is not represented in the data on n-

hexane use but is reported in other categories in the statistics, with the statistical data for fuel.

Solvent extraction of vegetable oils and defatting of fishmeal

n-Hexane or hexane mixtures rich in n-hexane are used for the extraction of vegetable oils from

various seeds and crops to obtain a higher yield of oil from the seeds than a mechanical screw press

allows. In the 1970s, it was estimated that soybean oil extraction accounted for approximately 30%

of all uses of n-hexane in the US. The oil is used for nutrition but also for production of bio diesel.

In the extraction process, vegetable oil is mixed with cooled hexane in a fractionation plant. Part of

the oil will crystallize as a solid that can be filtered from the liquid part. After the solid part has been

melted, hexane is removed by evaporation. Hexane is circulated in a closed system and reused.

Solvent extraction with hexane is also used in the fish industry to reduce the fat content in the meal

from certain fish. According to FAO (1986), reduction of the oil content from 10% to 1% in menha-

den, pilchard or anchovy meal would require about 4 litres of hexane per kilogramme of meal.

Hexane is listed in part II of Annex 1 to the EU Directive 2009/32/EC on extraction solvents used in

the production of foodstuffs and food ingredients. The Directive provides maximum limits for re-

sidual hexane in the products (see chapter 2). Hexane is defined in the Directive as follows: “Hex-

ane means a commercial product consisting essentially of acyclic saturated hydrocarbons contain-

ing six carbon atoms and distilling between 64 °C and 70 °C. The combined use of Hexane and

Ethylmethylketone is forbidden”. This definition excludes 3 of the 4 hexane blends that have been

registered under REACH because of their boiling range and only leaves the pure n-hexane and one

of the n-hexane rich blends registered under list number 930-397-4 as possible hexanes for extrac-

tion of food materials.

Some of the use of n-hexane in this industry might have been reported to the Danish Product Regis-

ter under a different CAS number as a broader mix of hexanes.

In laboratories

n-Hexane is used as an extractant for non-polar compounds and in calibration of instruments for

analysis of volatile organic compounds (VOCs) and total petroleum hydrocarbons (TPHs). To obtain

a high grade of purified n-hexane laboratories sometimes carry out their own fractionated distilla-

tion but many products are available from the traditional suppliers to laboratories.


Blowing agent

n-Hexane is used as a physical blowing agent in a number of plastic foams like PU (polyurethane)

foam for thermal insulation, PET (polyethylene terephthalate) foam and acrylic plastic. Other sub-

stances that are used for the same purpose are HCFC 142b, HFC 134 A, iso-pentane, n-heptane,

CO2, N2. It should be noted that HCFC 142 is covered by the phaseout schedule according to the

terms of the Montreal Protocol and its amendment calling for a 90% reduction in consumption in

2015, 99.5 % in 2020 and 100 % in 2030 (US EPA, HCFC Phaseout Schedule).

Reaction Medium

n-Hexane is used in the production of polyethylene as reaction solvent or slurry liquid phase for

several commercial polyethylene processes. n-Hexane is similarly used as a reaction solvent in sev-

eral commercial polypropylene processes. In these processes, n-hexane is enclosed in a reaction

system and continually recycled, with minimal loss.

A technical grade of hexane, containing 47% n-hexane and 53% mix of 4 other C6 aliphatics is used

as the reaction solvent in the production of diethyl- and dimethylthiophosphorylchloride, both

intermediates for the production of some organophosphate insecticides.

Special purpose solvent and cleaning agent (degreaser)

n-Hexane is used in adhesives, sealants, binders, fillers, lubricants, paints and coatings, brake

cleaners, degreasers and in cleaners used in the printing industry (rotogravure and flexo) as further

described in section 3.3.3. As solvent in rubber (adjustment of the viscosity of the rubber used for

tire production), rubber cement and in adhesives like those used for shoe making and repair, adhe-

sives for holding the ends of tin cans, adhesives used in the production of balls used in several

sports, and in adhesives used for production of tapes, bandages and dressings (Environment Cana-

da, 2009; ECHA Dissemination Database: Registration Dossier for n-hexane).

The US Household Products Database from the National Library of Medicine lists 85 consumer

products containing n-hexane with typical concentrations between 5 and 20 %. The products are

mainly adhesives (spray or liquid), cleaners and miscellaneous car maintenance products.

n-Hexane is listed on the list of propellants and solvents that are permitted in aerosols up to 1 litre

in Denmark.

The use of n-hexane as degreaser was in the global news in 2011 because a large number of Chinese

workers at a supplier to Apple were poisoned from the use of the substance to degrease the touch

screen panels that are produced for tablets (New York Times, 22 February 2011). A total of 137 cases

of n-hexane poisoning were also mentioned in the 2011 report on Supplier Responsibility from

Apple Inc. (2011).

Other uses

A number of additional uses are reported including:

carrier or propellant in perfumes (n-hexane may not be used in cosmetic products in Europe.

But as listed below, n-hexane has been registered under REACH with the use in perfumes and

fragrances as well as for personal care products for private use)

in the manufacture of veterinary medicinal ingredients

in non-mercury low temperature thermometers

denaturing agent

to help shape pills and tablets in the pharmaceutical industry.

The uses of hexane as registered under REACH are summarized in Table 7. As described earlier,

there exists a long range of consumer uses comprising, amongst other, use in adhesives, sealants,

anti-freeze and de-icing products, coatings and paints, thinners, and paint removers.


TABLE 7

USES IN EUROPE REPORTED IN THE REACH REGISTRATIONS (ECHA DISSEMINATION DATABASE, REGISTRATION

DOSSIER FOR N-HEXANE)

Manu-

facture

Formu-

lation

Uses at

indu-

stri-al

sites

Profes-

sional

use

Consu-

mer use

Manufacture of substance ✔ ✔

Distribution of substance ✔ ✔

Formulation & (re)packing of

substances and mixtures

✔

Polymer processing ✔ ✔ ✔

Use in a laboratory ✔ ✔ ✔

Use in coatings ✔ ✔

Use in cleaning agents ✔ ✔

Blowing agents ✔ ✔

Functional fluids ✔ ✔

Mining Chemicals ✔

Used as a fuel ✔

Adhesives, sealants ✔

Anti-freeze and de-icing products ✔

Biocidal products (e.g. disinfect-

ants, pest control)

✔

Coatings and paints, thinners,

paint removers

✔

Fillers, putties, plasters, modelling

clay

✔

Finger paints ✔

Non-metal-surface treatment

products

✔

Ink and toners ✔

Leather tanning, dye, finishing,

impregnation and care products

✔

Lubricants, greases, release prod-

ucts

✔

Perfumes, fragrances ✔

Polishes and wax blends ✔

Textile dyes, finishing and im-

pregnating products

✔

Cosmetics, personal care products ✔


According to the ECHA web site, the classification of n-hexane has been notified to ECHA by a total

of 2630 companies. This indicates the number of European companies that are using the substance

in products that they place on the market. (The seven companies that have registered n-hexane are

included in this number). This number does not give any information as to how many products that

are on the market containing n-hexane.

3.3.2 Consumption of n-hexane in EU

As mentioned in section 2.1.3, n-hexane is registered under REACH in the tonnage band 10,000 to

100,000 t/year.

No further information on n-hexane manufacturing or consumption volumes in the EU has been

identified.

3.3.3 Consumption of n-hexane in Denmark

Data on n-hexane registered in the Danish Product Register were retrieved in March 2014.

The Danish Product Register includes hazardous chemical substances and mixtures which are pro-

duced or imported for professional use in quantities of 100 kg or more per year. Hazardous sub-

stances and mixtures include:

Substances and materials that are classified as hazardous under the Danish Ministry of the

Environment's regulations, or contain 1% or more of a substance classified as hazardous to

health or environment.

Substances and mixtures assigned an occupational exposure limit in the WEA list of Limit

Values for Substances and Materials.

Mixtures that contain 1% or more of a substance that has been assigned an occupational expo-

sure limit in the WEA list of Limit Values for Substances and Materials

The data from the publicly available part of the Danish Product Register (SPIN database) show that

the main non-confidential uses of n-hexane are as solvent, in degreasers and, in minor amounts in

miscellaneous products like cleaning and washing agents, paints and varnishes, adhesives, lubri-

cants, anti-corrosion materials, casting slips for plastic, process regulators.

The non-confidential uses add up to 11.9 tonnes in 2011, while the total consumption is reported to

be approximately 246 tonnes. The total has been relatively stable since 2000 except in 2002 and

2003 where the consumption increased to 942.6 and 955.8 tonnes respectively. The data in general

indicate that the majority of the consumption is by a few users and the actual use of the substance is

confidential.

Data from 2012 from the Product Register show a total of approximately 243 tonnes.

Solvent

In Denmark, the solvent extraction with hexane is used by at least one company, Aarhus Karlshamn

(AAK), which is one of the world's leading producers of high value-added speciality vegetable fats.

The company confirms that they are using hexane for extraction in the production of rapeseed and

other vegetable oils. In the case of rapeseed oil, the clean seeds are steamed and crushed into thin

flakes in a rolling mill. The flakes are heated up before the fat is pressed out. Any remaining oil in

the cake is extracted with the help of hexane, which is recycled in a condensation process. The rape-

seed oil gained by this extraction is cleaned of any residual hexane. The amount of hexane used is

about 1 kg hexane per ton of seeds (raw material) (AAK, 2014). Another Danish producer of rape-

seed oil has informed that they do not use solvent extraction. One of the Danish manufacturers of

edible oil informs in their environmental permit that they use 70 tonnes of hexane per year (mass

balance).


Hexane, primarily in the form of iso-hexane, is also used in Denmark in small amounts for solvent

extraction in the production of fishmeal and fish oil. Denmark is the seventh biggest fishmeal pro-

ducing country in the world and the fourth biggest producer of fish oil. There are currently three

remaining fishmeal production sites along the West coast of Denmark and one on the Faroe Islands.

The average Danish production of fishmeal over a 5-year period (2008-2012) was 160,000 t/year

and the average production of fish oil from 2008-2012 was 60,000 t/year. The production in 2012

was unusually low (less than 80.000 t fishmeal and ca. 30.000 t fish oil) due to very low fishing

quotas (Marine Ingredients Denmark, 2014). However, the solvent extraction method which is only

carried out by one company in Denmark, specialised in production of marine phospholipids, is only

applied when the levels of dioxin in fish is above a certain level. Only 2,000 t/y have been treated in

the period 2008 – 2012 and facility has only been running for 14 days/y. The volume of hexane in

the extraction facility is 60 m3. The used hexane is condensed and recycled. Residues in the prod-

ucts constitute 5 – 10 ppm in fish meal and 1 ppm in fish oil. It is planned to change the production

to health food products which will at the same time mean that solvent extraction must be carried

out with pure n-hexane (Polar Omega a/s, 2014).

A technical grade of hexane is used as the reaction solvent in the production of two intermediate

products for organophosphate insecticides. The production process is applied large scale at Chemi-

nova in Denmark where most of the hexane is regenerated. During the purification process, n-

hexane is distilled from the reaction mixture and condensed, and the remaining n-hexane in the

process air is recovered using active carbon pellets. 60 % of the remaining n-hexane in the process

air bind to the carbon pellets and are afterwards released, collected and re-utilised in the produc-

tion; 40% is incinerated. In 2012, the amount regenerated was 720 tons of hexane saving the com-

pany more than half a million Danish kroner (Krogh and Jensen, 2014).

The amounts of n-hexane used for non-confidential uses as solvent reported to the Danish Product

Register for the period 2000 to 2011 are shown in Figure 1 (SPIN, 2013). Recycling of n-hexane

used as an extraction solvent is most likely part of the explanation for the variation in consumption.

FIGURE 1

USE OF N-HEXANE AS SOLVENT IN DENMARK. AMOUNTS REGISTERED IN 2005 AND 2005 ARE 1 TONNE AND 0.6

TONNES, RESPECTIVELY. (DATA FROM SPIN DATABASE).

Fuels for engines

The amounts of gasoline ('motorbenzin' in Danish) with the CAS no. 86290-81-5 registered in the

Danish Product Register for the period 2000 to 2011 are shown in the following figure.

0

100

200

300

400

500

600

700

2001 2002 2003 2004 2005 2006 2007 2008 2009 2010 2011

Us

e a

s s

olv

en

t (t

on

ne

s)

Registeret amounts of n-hexane, solvent use (SPIN data)


FIGURE 2

REGISTERED AMOUNTS OF GASOLINE ("MOTORBENZIN" IN DANISH), CAS NO. 86290-81-5, CONTAINING < 5 % N-

HEXANE. (DATA FROM SPIN DATABASE)

Safety data sheets for gasoline as registered in the SPIN database typically report that the content of

n-hexane is <5 % which corresponds to the concentration of 1–3 % as reported for unleaded gaso-

line.

According to information from EOF (the industry association for oil companies in Denmark – in

Danish: Energi- og Olieforum), the consumption of gasoline in 2012 was a little less than 2 million

m3 (EOF, 2014). This corresponds to 2 million litres which would theoretically contain approxi-

mately 45,000 tonnes of n-hexane assuming a density of 0.75 and a maximum content of 3 % n-

hexane. The gasoline consumption in 2012 is comparable to the gasoline consumption in 1986.

Through the 1980's and 1990's the consumption has increased and then gradually decreased again

through the 2000's.

As mentioned in the ATSDR profile (ATSDR, 1999), the dual role of n-hexane as a component of

refined petroleum fuels and as a highly refined, specialized product for other end-uses lead to com-

plications in making estimates of actual production levels. No formal production statistics were

identified associated with the n-hexane contained in heating or motor fuels from companies docu-

mented as producing appreciable amounts of n-hexane for commercial use.

Other uses

Other uses are shown in Figure 3 and comprise applications in adhesives, paints and varnishes, as

well as cleaning agents.

0

500000

1000000

1500000

2000000

2500000

3000000

3500000

2000 2001 2002 2003 2004 2005 2006 2007 20082009 2010 2011

To

nn

es

Registered amounts of gasoline (SPIN data)


FIGURE 3

USE OF N-HEXANE IN DENMARK ACCORDING TO USE CATEGORY (DATA FROM SPIN DATABASE)

Consumer products

Consumer products that contain small amounts of n-hexane include gasoline, rubber cement, type-

over correction fluids, non-mercury (low temperature) thermometers, alcohol preparations, and

aerosols, and perfumes. n-Hexane is also a component of preparations such as paint thinners, gen-

eral-purpose solvents, degreasing agents, and cleaners. (NPI, 2014).

Internet search for Danish safety data sheets for products also available for the consumer, show that

e.g. glues, lubricants, water proofing sprays and spray paints, and also different car care products

contain small amounts of n-hexane, typically below 1%, but in some cases up to 5 % and even high-

er. Concentrations of up to 25% are seen in different products likely to be used by both consumers

and professionals such as certain multipurpose grease products used for car and machinery

maintenance and repair work.

N-hexane is used also as a carrier and extraction solvent in manufacture of fragrances for other

purposes than cosmetics and may therefore be found in small amounts in scented products.

3.4 Historical trends in use

3.4.1 EU

N-hexane has been extensively used in the industry for decades, alone or mixed with other solvents,

and has also been utilised in many consumer products. However, observations of n-hexane neurop-

athy in workers with repeated exposure in the shoe manufacturing industry already in the 1950's

followed by many case stories from both industrial settings with poor ventilation and e.g. among

glue sniffers, along with the high volatility of the substance have made n-hexane a subject for sub-

stitution.

Many companies have over the years voluntarily, or supported by regulatory requirements or cus-

tomer demands, taken initiative to substitute n-hexane with other less hazardous substances in

both industrial settings and in consumer products.

No statistical data have been identified to illustrate the development.

3.4.2 Denmark

The total consumption of n-hexane in Denmark is given in Figure 4. According to the data available

from the SPIN database, the yearly consumption did not change significantly, varying between 250

and 360 t/y during the period from 2005 – 2011. Available data from the Danish Product Register

(SPIN) indicates that the total use of n-hexane in Denmark (reported as the pure n-hexane) has

stayed almost constant the last 3 years. There was a peak of use in 2002 and 2003 which, based on

the data seems to be from the use as solvent.

02468

10121416

Us

e p

er

na

tio

na

l u

se

c

ate

go

ry

(to

ns

) Use of n-hexane in Denmark (SPIN data)

Paints and varnishes

Adhesives

Cleaning and washing agents

Others


The data further demonstrate that the total number of products containing n-hexane and placed on

the Danish market or imported has decreased steadily since 2001 with a peak in 2002, 2003 and

2004. Only 250 products containing n-hexane were registered in 2011 (data not shown).

FIGURE 4

TOTAL USE OF N-HEXANE IN DENMARK (DATA FROM SPIN DATABASE)



fractions from the refinery process. The total registered manufacture and import of n-hexane in the

EU are indicated to be within the tonnage band 10,000-100,000 t/y.

In the trade statistics n-hexane is included in broader commodity codes and therefor no specific

data on import/export for n-hexane or for the technical blends of hexanes have been identified.

Due to its technical properties n-hexane is used for a wide variety of products and processes. Except

for its presence in fuels for engines, the major use in Denmark is as an extraction solvent used in

manufacture of vegetable oils, and as a reaction solvent in manufacture of pesticides. Hexane is

recovered and recycled in both production processes.

According to information from the Product Register considerably smaller amounts are used in

cleaning and washing agents, adhesives, lubricants, and corrosion inhibitors.

N-hexane is also present in a number of different consumer products such as glues, lubricants,

water proofing sprays, spray paints, car care products, and certain scented products. Concentra-

tions are typically below 1 % but higher concentrations up to ca. 25 % are seen in products for

maintenance and repair of cars and machinery which may also be used by consumers.

N-Hexane has been the focus for substitution for many decades, but no statistical data have been

identified to illustrate the development.

0

200

400

600

800

1000

1200

2001 2002 2003 2004 2005 2006 2007 20082009 2010 2011

To

tal

us

e (

ton

s)

Total use of n-hexane in Denmark (Spin data)


4. Waste management

4.1 Waste from manufacture and industrial use of n-hexane

n-Hexane is not manufactured in Denmark and therefore no waste from manufacturing of the sub-

stance is generated.

The major use of n-hexane in Denmark is as a solvent in the production of vegetable oil, fish oil,

fishmeal and organophosphate insecticides. In these production processes n-hexane is recovered or

incinerated with process air if not possible to recover. Some n-hexane is released to air, e.g. from

the production of vegetable oil, according to the environmental approval for a new facility for frac-

tionation of oil using cooled down hexane (Miljøcenter Århus, 2008) and some n-hexane mixed

with other substances is also disposed of as waste.

Hexane is highly flammable; therefore n-hexane or mixtures with significant amounts of n-hexane

are classified as hazardous waste.

In Denmark, waste containing hexane from manufacturing processes will typically be collected and

treated as organic chemical waste which is incinerated (either on-site or by Nord) and the substance

is completely destroyed. However, it is expected that hexane will evaporate during production or

use of the product and therefore only small amounts will end up in the waste stream.

4.2 Waste products from the use of n-hexane in mixtures and articles

Due to its classification (section 2.1.2) and in accordance with the Danish Statutory order on waste

(BEK no. 1309 of 18/12/2012) Annex 4, products and mixtures containing n-hexane must be dis-

posed of as hazardous waste if they contain more than 0.5% n-hexane.

In Denmark, waste containing hexane will typically be collected and treated as organic chemical

waste, in which case the waste is incinerated and the substance is completely destroyed.

Due to the volatile properties of the substance, n-hexane will most likely have evaporated from any

articles containing residues of the substance.

4.3 Release of n-hexane from waste disposal

No studies regarding release of the substance from disposal of waste containing the substance have

been identified. Release from incineration is not relevant.


N-Hexane is a highly volatile chemical which will tend to evaporate during production and use. It is

therefore not likely to end up in the waste streams in any considerable amounts.


5. Environmental effects and exposure

5.1 Environmental fate

5.1.1 Degradation

Abiotic degradation

Photodegradation is not considered a relevant degradation pathway, since n-hexane does not ab-

sorb ultraviolet light. The dominant atmospheric removal mechanism for n-hexane is generally

regarded to be decomposition by hydroxyl radicals. Calculations assuming typical hydroxyl radical

concentrations have suggested a half-life of approximately 2.9 days (ATSDR 1999).

n-Hexane can react with nitrogen oxides to produce ozone precursors under controlled laboratory

conditions, however, the smog-producing potential of n-hexane is evaluated to be very low com-

pared to that of other alkanes or chlorinated VOCs.

Hydrolysis is not a relevant degradation mechanism as n-hexane, similar to other alkanes, is re-

sistant to hydrolysis (ATSDR 1999).

ECHA’s registration data for n-hexane do not comprise data on abiotic degradation.

Biodegradation

With respect to biodegradation, the attention is generally on complex mixtures of hydrocarbons,

which will be present at, e.g., oil spills. In such situations the heavier fractions or less volatile (usu-

ally C10 or longer chain alkanes, aromatics, and/or polycyclic aromatics) are of greater concern

than the lighter constituents.

A read-across study on biodegradation of naphtha (mainly consisting of C4 - C11 alkanes) is availa-

ble from ECHAs registration data on n-hexane. 98 % of the test substance was degraded at the end

of 28 days, and 83% was degraded at the end of the 10 -day window. Therefore, n-hexane is evaluat-

ed to be readily biodegradable and does not inhibit biodegradation. The conclusion is supported by

a QSAR study on hexane.

Generally, unless n-hexane is buried in deeper layers of a soil or sediment, volatilization is assumed

to occur at a much higher rate than any biotic or abiotic degradation processes.

In deeper soil layers or sediments, n-hexane may be fairly persistent. This is due to slow chemical

hydrolysis and limited potential for biodegradation under anoxic and/or nutrient-poor (N, P) condi-

tions.

5.1.2 Distribution

The physical properties of n-hexane determine its transport and partitioning in the environment.

The dominant transport process from water is volatilization. The US EPA estimated half-lives for n-

hexane in water with any degree of turbulent mixing (e.g. rivers) at 3 hours, and no longer than 6.8

days for standing bodies of water (e.g. small ponds) (ATSDR 1999).


In soil, the dominant transport mechanism for n-hexane close to the surface can likewise be ex-

pected to be volatilization considering the low water solubility (0.0098 g/L) and high vapour pres-

sure (10 kPa), even though binding to the soil organic matter might be significant in organic soils.

No experimental information focusing directly on n-hexane transport in soil is available (ATSDR

1999).

The low density of the substance (0.66 g/mL) suggests a low potential for leaching into deeper soil

layers, since nhexane would tend to float on top of the water-saturated zone (also called light non-

aqueous phase liquid, LNAPL).

Experimental data on bioaccumulation are not available. Based on the log octanol/water partition

coefficient (log P = 3.3 - 4) and the estimated log sorption coefficient (log KOC = 2.9 – 3.6, ATSDR

1999), n-hexane is not concentrated to a large extent in biota. A calculated bioconcentration factor

(BCF) of 453 for a fathead minnow suggests a relatively low potential for n-hexane to bioconcen-

trate or bioaccumulate in trophic food chains (ATSDR 1999). The calculated BCF is also far below

the REACH PBT bioaccumulation criterion of 2000 for aquatic species.

5.2 Environmental hazard

5.2.1 Classification


TABLE 8

ENVIRONMENTAL CLASSIFICATION OF N-HEXANE ACOORDING TO ANNEX VI OF REGULATION (EC) NO 1272/2008

(CLP REGULATION).


chemical

identification

CAS No Classification

Hazard Class and

Category Code(s)

Hazard statement

Code(s)

601-037-00-0 hexane 110-54-3 Aquatic Chronic 2 H411

5.2.2 Environmental effects

Aquatic toxicity

A number of ecotoxicity tests are available from the US EPA ECOTOX database (2014).

The lowest effect concentrations for each organism group are presented in Table 9.

14 acute fish studies are listed in the ECOTOX database covering the freshwater species Oryzias

latipes, Pimephales promelas, Pleuronectes ferrugineus, Oreochromis mossambicus, and Leucis-

cus idus, as well as a single saltwater species, Oncorhynchus kisutch. The most and least sensitive of

the tested species appear to be Pimephales promelas with an LC50 of 2.5 mg/L, and Oryzias latipes

with an LC50 of > 10,000 mg/L, respectively.

For aquatic invertebrates, studies on both fresh- and saltwater are presented, covering 7 species

(Artemia salina, Cyclops viridis, Homarus americanus, Daphnia magna, Tetrahymena pyriform-

is, Brachionus calyciflorus, Brachionus plicatilis). The effect concentration range for the saltwater

species was 1.5 to 154 mg/L, while the EC50 for freshwater species ranged from 3.8 to > 1000 mg/L.

EC50 values are available for six species/genera of alga (Anabaena sp., Chlamydomonas angulosa,

Chlorella sp., Nostoc sp., Macrocystis pyrifera, Skeletonema costatum). Two marine organism

studies (from 1964 and 1977) reported photosynthesis effects on Macrocystis pyrifera (large brown

algae) and Skeletonema costatum (a diatom) at 10 mg/L and 0.3 mg/L, respectively. The latter


study was a field study and is therefore not comparable with the other studies. The six remaining

studies report growth inhibition or physiological effects at EC50 ranging from 8.1 – 52,800 mg/L.

Further, aquatic tests were made with snails; Melanoides tuberculata, LC50 = 1,900 mg/L, and

Crassostrea giga, which showed abnormal development effects in the concentration range 10 –

10,000 mg/L.

With respect to sediment dwelling organisms, tests with a worm (Branchiura sowerbyi) and an

insect species (Chironomidae) indicate that these animals are less susceptible (effect concentration

≥ 595 mg/L).

Thus, the lowest effect concentration of 1.5 mg/L has been determined in a test with the small crus-

tacean Artemia salina. However, for all organism groups the effect concentrations range over sev-

eral orders of magnitude, which is supposedly related to methodological issues and not to toxicity

mechanism of n-hexane.

In most cases, the effect concentrations listed in the database exceed the water solubility of n-

hexane, which is about 10 mg/L. It is usually not reported, if a solvent is used to achieve the stated

test concentrations. Likewise, set-up of the system (static system or flow-through) influences the

study results. All studies on aquatic toxicity listed in the ECOTOX database were static studies apart

from the freshwater fish study on Pimephales promelas. In static test systems, part of the test mate-

rial is likely to evaporate before the end of the exposure period, rendering the actual exposure lower

than the nominal concentration.

Actual exposure concentrations are therefore unknown. Also possible toxicity interactions of n-

hexane and a possible solvent are not known. In conclusion, the reported effect concentrations

should be interpreted very cautiously.

TABLE 9

OVERVIEW OF DATA ON TOXICITY OF N-HEXANE TO AQUATIC ORGANISMS IN LABORATORY STUDIES (DATA FROM

THE US EPA ECOTOX DATABASE)

Group Species Study type* Endpoint* Value

(mg/L)

Fish, freshwater Pimephales promelas 96 h, flow-through LC 50 2.5

Fish, marine Oncorhynchus kisutch 96 h, static NR 100

Invertebrates,

freshwater

Daphnia magna 48 h, static EC50 3.8

Invertebrates,

marine

Artemia salina 24 h, solvent; 2-

Propanone, static

EC50 1,5

Algae, freshwater Chlamydomonas angulosa 3 h, static EC50 on photo-

synthesis

8.1

Algae, marine Macrocystis pyrifera 48 - 96 h, NR EC50 on photo-

synthesis

10

* NR – not reported.

Terrestrial toxicity

No laboratory toxicity tests for terrestrial organisms were available.


5.3 Environmental exposure

5.3.1 Sources of release

n-Hexane is a component of refined petroleum products, therefore there is considerable potential

for releases to environmental media through the use of fuels for heating or transportation.

Its physical properties as a light alkane make it most suitable for use in gasoline, while it can also be

a minor constituent (less than 1% by weight) of other petroleum products. For modern gasoline

mixtures, the total percentage by weight of the n-hexane component is approximately 3% (ATSDR

1999).

Gasoline use can result in a variety of atmospheric emissions of n-hexane due to evaporation during

refuelling and storage, and exhaust releases in case of incomplete combustion. In its review, ATDSR

(1999) evaluates the largest release of hexane to be to air due to the volatility of the substance.

Releases to water may happen from a number of sources including industrial discharges, effluents

from municipal waste-treatment plants, and nonpoint-source runoff from roads and other surfaces.

n-Hexane can be released to soil or sediments from spills, during the landfilling of sludge and other

wastes generated from industrial processes, as well as municipal sewage treatment (ATSDR 1999).

Industrial releases of n-hexane in Europe have been assigned to the following environmental re-

lease categories according to ECHA registration data (January 2014):

ERC 1: Manufacture of substances

ERC 2: Formulation of preparations

ERC 3: Formulation in materials

ERC 4: Industrial use of processing aids in processes and products, not becoming part of articles

ERC 5: Industrial use resulting in inclusion into or onto a matrix

ERC 6d: Industrial use of process regulators for polymerisation processes in production of resins,

rubbers, polymers

Consumer products that contain small amounts of n-hexane are expected primarily to result in

releases to air.

5.3.2 Monitoring data

n-Hexane is not included in the Danish environmental surveillance programme, NOVANA. Howev-

er, urban background concentrations of the some ozone precursors have been measured in Copen-

hagen since 2009. The annual average concentration of n-hexane was 0.16 μg/m³ and the 90%

percentile was 0.27 μg/m³ in 2012. Figures from previous years are given in Table 10.

TABLE 10

ANNUAL CONCENTRATIONS BASED ON DAILY AVERAGES IN URBAN BACKGROUND MEASURED ON H.C. ØRSTEDS

INSTITUTE IN COPENHAGEN.

Number of

samples

Concentration in

air (μg/m³)

90% percen-

tile Year Reference

200 0.15 0.31 2009 Ellermann et al. 2010

216 0.19 0.36 2010 Ellermann et al. 2011

307 0.19 0.33 2011 Ellermann et al. 2012

246 0.16 0.27 2012 Ellermann et al. 2013


5.4 Environmental impact

Reviews containing environmental impact assessments are currently not available and it is beyond

the scope of this survey to provide an environmental risk assessment of hexane. The environmental

properties of hexane are summarised in section 5.5.

The Danish soil quality criterion for volatile hydrocarbons (C6 –C 10) from oil or gasoline products is

25 mg/kg. The groundwater quality criterion is 9 µg/litre for the sum of hydrocarbons (C6 – C35).

(Danish EPA, 2014). The guideline value (B-value) for industrial air pollution is 0.4 mg/m3 (Danish

EPA, 2002). National emission ceilings for certain atmospheric pollutants and certain processes are

also relevant in relation to n-hexane.



n-Hexane has a low water solubility (0.0098 g/L) and high vapour pressure (10 kPa). Atmospheric

removal through reaction hydroxyl radicals might therefore be the most important abiotic degrada-

tion process. By means of a read-across study on biodegradation of naphtha (mainly consisting of

C4 - C11 alkanes), hexane was evaluated to be readily biodegradable.

Experimental data on bioaccumulation are not available. However, based on the log P (= log KOW =

3.3 - 4), an estimated log KOC of 2.9 – 3.6, and an estimated BCF of 453, n-hexane is not expected to

bioconcentrate or bioaccumulate significantly in trophic food chains.

Acute aquatic toxicity data are available from the US EPA ECOTOX database, while there is a gen-

eral lack of chronic and terrestrial data. The lowest acute toxic effect concentration of n-hexane was

determined at 1.5 mg/L in a test with the small crustacean Artemia salina. However, for all aquatic

organisms the reported effect concentrations cover several orders of magnitude, which is most like-

ly related to methodological problems and requires very careful interpretation of the listed effect

concentrations.

There is considerable potential for releases of n-hexane to environmental media through the use of

fuels for heating or transportation. Atmospheric emissions of n-hexane are due to evaporation dur-

ing processing of the substance or due to incomplete combustion of fuels. Other releases include

industrial discharges, effluents from municipal waste-treatment plants, and nonpoint-source run-

off, spills, sludge and other waste deposition.

Quantitative data on emissions to environmental compartments in Denmark or Europe could not be

identified. Consumer products that contain small amounts of n-hexane are expected primarily to

result in releases to air.

In Denmark, urban background concentrations of n-hexane have been measured since 2009 in

Copenhagen, because of the substance’s identification as an ozone precursor. The measurements

have been relatively stable with an average of 0.15 to 0.19 µg/m3.


6. Human health effects and exposure

6.1 Human health hazard

6.1.1 Classification

n-Hexane is subject to harmonised classification as a toxic to reproduction (cat. 2), harmful if swal-

lowed (cat. 1), toxic to organs through repeated or single exposure (cat. 2 and cat. 3, respectively),

and as a skin irritant (cat. 2) (Table 11).

TABLE 11

HARMONISED CLASSIFICATION ACOORDING TO ANNEX VI OF REGULATION (EC) NO 1272/2008 (CLP REGULATION)


chemical

identification

CAS No Classification

Hazard Class and

Category Code(s)

Hazard statement

Code(s)

601-037-00-0 hexane 110-54-3 Repr. 2

Asp. Tox. 1

STOT RE 2 *

Skin Irrit. 2

STOT SE 3

H361f ***:

H304

H373 **

H315

H336

* Minimum classification for a category.

** Hazard statement not specifying the route of exposure as the necessary information is not availa-

ble.

*** ‘Suspected of damaging fertility or the unborn child’. According to the criteria, the general haz-

ard statement can be replaced by the hazard statement indicating only the property of concern,

where either fertility or developmental effects are proven to be not relevant.

6.1.2 Toxicokinetics

Toxicokinetic data are based on the toxicological review on hexane from the US EPA (2005).

Oral exposure studies evaluating absorption of n-hexane in humans or laboratory animals are not

available. However, absorption following oral exposure can be determined by identification of n-

hexane and its metabolites in expired air, serum, and urine. Several studies indicating oral absorp-

tion are available.

Evidence of absorption upon inhalation exposure in humans is also limited, but has been investi-

gated in studies with exposed workers. Absorption rates were estimated at 17 – 24 %.

Several inhalation studies in humans and animals demonstrate the distribution of n-hexane. The

following partition coefficient values were calculated: olive oil: air, 146; blood: air, 0.80; and 1.0,

2.8, 5.0, 5.0, 3.0, 5.2, and 104 for lung, heart, muscle, brain, kidney, liver, and fat: air, respectively.


These values correspond to those values reported in other studies and clearly present n-hexane

affinity for fatty tissues. Blood levels of n-hexane have shown to decrease rapidly to approximately

half the steady state exposure values within the first 10 minutes and reached steady state levels by

100 minutes. The average half-life for n-hexane in blood was 1.5–2 hours.

No studies investigating the distribution of n-hexane following oral exposure in humans or labora-

tory animals are available.

In the liver, n-hexane is metabolized to various metabolites, which are then distributed in the blood

to various organs and tissues, including the liver, kidney, and brain. The primary metabolite, 2,5-

hexanedione, is believed to be the major toxic metabolite produced in humans. In rats, the primary

metabolite following inhalation exposure was 2-hexanol, followed by 4,5-dihydroxy-2-hexanone.

Several human inhalation studies have provided evidence for the elimination of n-hexane and me-

tabolites following occupational and voluntary exposures to n-hexane. The main route is via urine,

while alveolar excretion of n-hexane has been shown to account for 10% of the total uptake follow-

ing inhalation exposure. Occupational exposure studies have also shown that urinary concentra-

tions of 2,5-hexanedione may build up during the course of a workweek. Therefore, urinary levels

may not consistently reflect the ambient n-hexane exposure concentrations.

6.1.3 Acute and chronic effects

The US EPA (2005) has compiled a large number of epidemiological studies investigating the health

effects of n-hexane in occupational environments.

In many studies, inhalation exposure to hexane has been associated with incidences of headache,

hearing deficit, dysesthesia in limbs, reduced sensation, dizziness and sleepiness, and muscle weak-

ness. These symptoms are consistent with neurophysiological findings in exposed individuals, here-

under increased numbers of polyneuropathy cases and decreased nerve conduction velocity.

The relationship between the occurrence of intracranial tumours among employees at a petrochem-

ical plant and inhalation exposure to n-hexane and a number of other chemical compounds was

studied. No relationship was found between exposure to n-hexane and the occurrence of intracrani-

al tumours (US EPA, 2005).

Neurophysiological effects could also be determined in an occupational study with shoe workers

several months after exposure was stopped/reduced to trace amounts. Still, the previously exposed

workers showed increased signs of polyneuropathy compared to unexposed workers. Another study

with cases of polyneuropathy at a ball-manufacturing plant in Taiwan observed recovery of neuro-

logical symptoms in a follow-up at the factory 2 years after the ventilation system had been changed

and solvent operations including hexane handling were enclosed. Vision changes in relation to n-

hexane exposure have also been reported in several studies, amongst other impaired colour vision

and maculopathy.

A few studies investigated the effects of n-hexane on the immune system with contradicting conclu-

sions. A significant inverse correlation also was found between the immunoglobulin levels and the

2,5-hexanedione concentrations in the exposed group, while no differences were detected in white

blood cell counts, natural killer cytotoxic activity and serum levels of interleukin-2 between exposed

and unexposed subjects (US EPA, 2005).

Consumers

Consumer exposure to n-hexane is not expected to give rise to major concern. Most consumer

products contain relatively low levels of n-hexane and are not used frequently. Some product types

such as adhesives, sealants and grease or special products used for car or machinery repair may


contain higher concentrations. These may result in high short-term exposures, but are expected to

be used infrequently.

Scented toys may release n-hexane as demonstrated by a Danish consumer survey. Although the

specific product is no longer on the market there is a possibility that children may be exposed to

small amounts of n-hexane over a shorter period of time from scented products like this. As n-

hexane has low acute toxicity, no significant effects are expected this exposure.

6.1.4 Reproductive toxicity

A number of animal studies investigated reproductive and developmental effects of hexane expo-

sure. Various stages of atrophy of the testicular tissue (incidence and severity of effect not reported

by the study authors) following oral administration of hexane metabolites and a high dose of n-

hexane (3980 mg/kg-day) was reported in rats. An inhalation study with rats also observed testicu-

lar lesion as an effect of repeated hexane exposure, however, the lesions were partly reversible.

Sperm morphology and reproductive index were not affected in male mice following exposure to

hexane vapour. Several inhalation studies concluded that n-hexane has little or no effect on repro-

duction and development of rats or mice (US EPA, 2005).

An oral exposure study with mice dams reported no reproductive, developmental, or teratological

effects of n-hexane in mice dosed with n-hexane by injections up to 2200 mg/kg/day. First at signif-

icantly increased concentrations (7920 and 9900 mg/kg/day), detrimental effects were observed.

Therefore the authors suggested that n-hexane is not teratogenic at concentrations associated with

overt maternal toxicity. Spermatoxic tests showed no change in parameters in rats orally exposed to

n-hexane (US EPA, 2005). A selection of study results on reproductive and developmental effects is

presented in Table 12.

TABLE 12

EFFECT CONCENTRATONS FOR EFFECTS ON REPRODUCTION (DATA FROM US EPA, 2005).

Organism Exposure conditions Effect Effect

level

Concentration

Mice Oral, daily dose, gestation

day 6-15

Reproductive, develop-

mental, or teratological

effects

NOAEL 2200 mg/kg bw


day 6-15

Dam mortality LOAEL 9900 mg/kg bw


day 6-15

Decreased fetal birth

weight

LOAEL 7920 mg/kg bw

Rats Oral, daily dose, 5 consec-

utive days

Spermatoxic effects (head

counts, sperm velocity,

sperm morphology, and

the histopathology)

NOAEL 10.000 mg/kg bw

Rats Inhalation, 20 h/day,

gestation day 6-19

Developmental effects NOAEL 200 ppm

Rats Inhalation, 6 h/day, gesta-

tion day 8-16

Decreased birth weight of

pups

NOAEL 1000 ppm


Organism Exposure conditions Effect Effect

level

Concentration

Mice Inhalation, 20 h/day,

gestation day 6-17

Decreased birth weight of

female pups

LOAEL 5000 ppm

Mice Oral, 20h/day, 5 consecu-

tive days

Effects on sperm mor-

phology

NOAEL 5000 ppm

6.1.5 Mode of action

Ultrastructural studies indicate that nervous system toxicity induced by n-hexane may be the result

of a sequence of events leading to degeneration of the axons. This sequence has been investigated in

after after repeated dose exposure and is described as follows (US EPA, 2005): “Sciatic, tibial, and

plantar nerves were investigated by light microscopy. The authors described focal condensation of

neurofilaments, mitochondria, and smooth endoplasmic reticulum with increase in the number of

neurofilaments. The earliest pathological indicator of peripheral nerve axonal degeneration was

axonal swelling in the distal nonterminal region of the large myelinated fibers. These axonal swell-

ings appeared first proximal to the nodes of Ranvier and ascended the nerve with further exposure.

Paranodal swelling was accompanied by shrinkage and corrugation of the adjacent distal internode.

Paranodal myelin sheaths split and retracted leaving giant axonal swellings near the nodes of

Ranvier. The study authors suggested that Schwann cells may become associated with these denud-

ed regions and remyelinate short segments. Remyelinated segments then mark the position of the

axonal swellings that were resolved without fibre breakdown or total internodal demyelination.”

Several studies suggest that the metabolite, 2,5-hexanedione, is the primary toxic agent by which n-

hexane brings about neurotoxicological effects. 2,5-Hexanedione has been shown to have approxi-

mately 38 times the neurotoxic potency of n-hexane (on an equimolar basis). The onset of distal

axonal degeneration following 2,5-hexanedione administration has been observed in rats, mice,

cats, and birds (US EPA, 2005). The mode of action is suggested to imply the binding of 2,5-

hexanedione to proteins, forming pyrrole adducts then undergoing oxidation, leading to protein

cross-linking. For example, 2,5-hexanedione was shown to cross-link neurofilaments proteins of

spinal cord when administered to male rats for 180 days in drinking at a concentration of 5000

mg/L.

A substantial body of physiological and biochemical studies in vitro and in vivo indicate that cross-

linking of neurofilamentous proteins takes place as a result of exposure to 2,5-hexanedione. A con-

sistent observation made between species, between adult and immature members of the same spe-

cies, and within individual humans and animals, was that longer axons in the peripheral nervous

system and central nervous system were more vulnerable to the toxic effects of n-hexane and its

metabolites than shorter axons. The axonal swellings that initially occurred proximal to nodes of

Ranvier in the most distal internodes of the longest axons were filled with disorganized masses of

neurofilaments (US EPA, 2005).

6.1.6 No effect-levels

Occupational exposure limit values

Occupational exposure limit values for n-hexane for selected European countries are presented in

Table 13.


TABLE 13

OCCUPATIONAL EXPOSURE LIMIT VALUES FOR N-HEXANE FOR SELECTED COUNTRIES (GESTIS DATABASE)

Limit value 8-hours Limit value short term

ppm mg/m3 ppm mg/m3

Belgium 20 72 - -

Denmark 20 72 2 x limit value (15

min)

2 x limit value (15

min)

European Union1 20 72 - -

France 20 72 - -

Germany 50 180 400 720

Sweden 25 90 50 180

The Netherlands 20 72 - 144

United Kingdom 20 72 - -

1 Indicative OEL (see Chapter 2)

Denmark has adopted the EU indicative occupational exposure limit values. However, as demon-

strated in Table 13, not all EU countries have chosen to adopt the EU indicative (non-binding) oc-

cupational exposure limit for N-hexane.

Derived no-effect levels and limit values

Derived no-effect levels for n-hexane registered under REACH are shown in Table 14. The DNELs

are from a joint submission and are established by the registrant for systemic effects from long term

exposure in the different exposed populations by inhalation or the dermal route, and for the general

population also from the dermal route. ECHAs dissemination website does not include the full justi-

fication behind the values. DNELs are used for risk assessment of specific exposure situations.

TABLE 14

DERIVED NO-EFFECT LEVELS (DNELS) FOR MTBE (ECHA, 2013A)

Population / -

route

Exposure Value Dose de-

scriptor / As-

sessment factor

Sensitive end-

point

Workers

- inhalation

Long term exposure

- systemic

75 mg/m³ LOAEC / 3 Neurotoxicity

Workers

- dermal

Long term exposure

- systemic

11 mg/kg bw/day NOAEL / 3 Neurotoxicity

General population

- inhalation

Long term exposure

- systemic

16 mg/m3 NOAEL / 5 Neurotoxicity

General population

- dermal

Long term exposure

- systemic

5.3 mg/kg bw/day NOAEL / 5 Neurotoxicity

General population

- oral

Long term exposure

- systemic

4 mg/kg bw/day NOAEL / 5 Neurotoxicity


6.2 Human exposure

6.2.1 Direct exposure

Consumers

Consumers are exposed primarily by inhalation but also dermal contact with different consumer

products containing n-hexane. Examples are adhesives, sealants, spray paints, silicon removers,

and water proofing sprays.

Maximum concentrations of n-hexane for different types of products according and publically avail-

able information as summarised by Environment Canada are shown in Table 15 together with use

conditions based on consumer product exposure model parameters (frequency of use and exposure

duration) from ConsExpo (Environment Canada, 2009).

TABLE 15

CONSUMER PRODUCTS CONTAINING N-HEXANE AND USE CONDITIONS BASED ON EXPOSURE MODEL PARAME-

TERS (ENVIRONMENT CANADA, 2009)

Consumer product Maximum conc. of

n-hexane in %

Frequency of use

(events/year)

Exposure duration

(min)

Construction Adhesive 30 2 240

Gasket Sealant 25 3 45

Spray Paint 20 2 20

Weatherstrip Adhesive 15 N/A N/A

Spray Adhesive 30 12 240

Weatherstrip Cement 8.9 7 16

The products listed in the table are primarily for professional use but may be used by consumers.

Most products specifically targeting the consumer market have typically lower concentrations of n-

hexane.

As part of the Danish EPA surveys on chemicals in consumer products, n-hexane has been found in

very low concentrations in cuddly toys for children in a consumer survey investigating the content

of sensitising substances as well as releases of certain volatile substances including n-hexane in

scented toys intended for children at the age of 0 to 10 years. Measurements of the emission from a

vanilla scented cuddly toy showed a release of n-hexane of 16 µg/m3 (Glensvig and Pors, 2006).

In another consumer survey from the Danish EPA investigating the release of chemical substances

from electric and electronic products, n-hexane was emitted from an electrical panel at concentra-

tions of 7.2 µg/unit/hour after 7 hours and <2 µg/unit/hour after 9 days (Mortensen, 2005).

No further data describing direct exposure to Danish consumers have been identified.

Occupational exposure

Occupational exposure to n-hexane and mixtures containing n-hexane include groups such as refin-

ery workers, shoe and footwear assembly workers, laboratory technicians, workers involved in ex-

traction of fish meal, fish oil and vegetable oils, workers involved in manufacture of pharmaceuti-

cals and pesticides, laboratory technicians, workers in textile and furniture manufacturing, workers

operating or repairing typesetting and printing machinery, workers in the electronics industry,

construction workers, carpet layers, carpenters, auto mechanics and gas station employees, workers

in plants manufacturing tires or inner tubes, and workers in air transport and air freight operations.


Due to the high volatility and flammability of n-hexane containment of the substance in industrial

settings is important. The odour threshold is reported to be approximately 60 ppm / 210 mg/m3

(IPCS, 1991) which is higher than the Danish occupational exposure limit of 20 ppm / 72 mg m3.

In Denmark, the major industrial uses involve recovering of the n-hexane and occupational expo-

sure is expected to be limited.

As n-hexane is a component in jet fuel, measurements of this substance among other VOCs were

made in Copenhagen Airport at Gate B4 in 2010 in order to monitor the occupational exposures of

workers in this area. The average concentration measured in the period 20.10.2010 to 17.11.2010

was 0.21 µg/m3 compared to the average urban background of ca. 0.20 at H.C. Ørstedsvej in Co-

penhagen (Ellermann et al., 2011).

No specific information on more recent occupational n-hexane exposures in Denmark have been

identified based on literature search and contact with the Danish Working Environment Authority.

6.2.2 Indirect exposure

Air

As mentioned in section 5.3.2, the average annual urban background concentrations of n-hexane in

2012 measured in Copenhagen was 0.16 μg/m³ and between o.16 and 0.19 μg/m³ in the period

2009 to 2012.

No other individual measurements of n-hexane in Denmark have been identified. n-Hexane may,

however also be included in measurements of total concentrations of volatile organic compounds.

Soil

n-Hexane has relatively low absorptivity to soil or sediment and releases to the environment are

expected primarily to end up in the air and water compartments. If spilled on the ground, the sub-

stance will evaporate or leach into the groundwater. Exposure via soil is therefore not considered

relevant.

Drinking water

No measurements of n-hexane in drinking water in Denmark have been identified. Drinking water

is not expected to be a relevant source of n-hexane exposure.

Food

Residues of n-hexane used from solvent extraction may be found in vegetable oils and fish oils for

consumption, typically at levels of approximately 1 ppm.

Environment Canada (2009) has estimated upper-bounding daily intake of –n-hexane from foods

based on the level of residual n-hexane typically found in refined vegetable oils (0.8 ppm). The

estimates are shown in Table 16.


TABLE 16

UPPER-BOUNDING DAILY INTAKE OF –N-HEXANE FROM FOODS BASED ON THE LEVEL OF RESIDUAL N-HEXANE

TYPICALLY FOUND IN REFINED VEGETABLE OILS (ENVIRONMENT CANADA, 2009)

Age group Percentile Intakes of vegetable fats and oils from

all food sources

(g/kg-bw/day) 1

Daily intake of n-hexane

(mg/kg-bw/day)

6-8 years 50% 0.73 0.58

90% 1.58 1.26

95% 1.81 1.45

19-30 years 50% 0.28 0.22

90% 0.71 0.57

95% 0.87 0.70

No measurements of n-hexane in Danish food have been identified.

Indoor climate

n-Hexane is often measured as part of the total concentration of VOCs in the indoor climate. No

measurements of n-hexane

Review of Canadian studies by Environment Canada (2009) showed that the highest concentration

of n-hexane in indoor air in a critical data set (Canadian studies in the 1990s-2000s) was 138

µg/m3 from a study conducted in Windsor, Ontario in 2006. This study was performed over a two

year period in 2005 and 2006, and the mean concentration of n-hexane ranged from 2.3 to 8.0

µg/m3. In other studies, the mean concentration of n-hexane ranged from 1.2 to 8.0 mg/m3.

No Danish indoor climate measurements of n-hexane have been identified.

6.3 Bio-monitoring data

Industrial hygiene surveys of occupationally exposed workers have shown good correlations be-

tween the extent of occupational exposure to n-hexane and the concentration of the metabolite, 2,5-

hexanedione in the urine. 2,5-Hexanedione is also the substance responsible for the effects on the

peripheral nervous system. To protect against the onset of subclinical and clinical neuropathological

symptoms of n-hexane exposure, ACGIH has proposed a BEI (Biological exposure index) of 0.4

mg/L as an acceptable concentration of 2,5-hexanedione in urine at the end of shift on the last day

of a workweek (EPA, 2005).

n-Hexane can also be measured in exhaled air. However, the short half-life of the substance means

that the concentration in exhaled air will only reflect the exposure situation immediately before the

measurement.

No results from biomonitoring of n-hexane in Denmark have been identified.


6.4 Human health impact

Workers

No information on exposure levels in the Danish work environment was available. A search in the

statistical data on industrial injuries available from the homepage of the National Board of Indus-

trial Injuries5 did not provide any hits for neither 'n-hexane' nor 'peripheral neuropathy'.

There is no indication that the existing risk reduction measures are not sufficient.

Humans exposed via the environment

The principal source of exposure to n-hexane is expected to be through inhalation of ambient and

indoor air. The DNEL for systemic effects from long term inhalation exposure for the general public

was 16 mg/m3 in the REACH registration dossier. When this DNEL is compared with the sum of the

average levels in ambient air in Copenhagen (1.6 – 1.9 µg/m3) and the average concentration levels

for indoor climate measured in Canadian studies (1.2 to 8.0 mg/m3) no major concern is identified.


n-Hexane is absorbed rapidly through the lungs in experimental animals and is widely distributed

in the body with an affinity for tissues high in lipid content. Particularly high levels have been found

in peripheral nerves. Dermal absorption is limited, but may be enhanced by other solvents. In hu-

mans, n-hexane is absorbed more slowly via the lung and very slowly through the skin.

n-Hexane has low acute toxicity. The critical effects of chronic exposure to n-hexane appear to be

testicular toxicity and neurotoxicity both to the central and peripheral nervous systems. Peripheral

neuropathy is well described after industrial exposure to n-hexane, particularly in shoemakers. The

testicular effects observed in rats have not been well documented in humans. Hexane is also irritat-

ing to skin.

2,5-Hexanedione is the main metabolite found in humans exposed to n-hexane and the substance

suspected of being responsible for the neurotoxicity of the substance and toxic effects in the testes.

The first symptoms of neurotoxicity are usually sensory and consist of tingling, numbness, burning,

or prickling sensations in the feet or toes followed by progressive muscle weakness first in the lower

and then upper extremities. Distal nerves are more commonly affected.

There is a large number of studies linking occupational exposure to n-hexane to the incidence of

peripheral neuropathy in humans particularly among shoemakers. However, few of these report air

concentrations, and where exposures are quoted, it is not clear whether they refer to n-hexane or to

commercial hexane. Also workers were exposed to mixtures of volatile solvents and the proportions

of n-hexane are not reported.

Denmark has adopted the EU indicative occupational exposure limit value of 20 ppm or 72 mg/m3.

No information on exposure levels relevant for Danish industrial uses is available. However, the

major applications of the substance as an extraction or reaction solvent take place in closed systems

and are less likely to result in significant workplace exposures.

Very limited data are available regarding consumer exposure in Denmark. As n-hexane is present in

several spray products and taking the volatility of the substance into account, consumers may be

exposed to relatively high concentrations on a short term basis. However, in general the consumers

are not expected to be exposed on frequent basis or for long periods of time, and are thereby not

expected to be at risk in relation to the long-term effects of n-hexane.

5 http://www.ask.dk/da/Statistik/Erhvervssygdomme-fordelt-pAa-diagnoser/2011.aspx


Indirect exposure can occur through air, drinking water and food. Urban air concentrations meas-

ured in Copenhagen of on average 0.16-0.19 µg/m3 do not give grounds for major health concerns.

No data on n-hexane in drinking water or food has been identified for the Danish situation. Data

from Canada estimating the total contribution from n-hexane containing food, in particular refined

vegetable oils, do not indicate any risk for the consumer. Based on the limited database, combined

exposures illustrating the Danish situation do not seem to be a concern in relation to the critical

effects of n-hexane.

Data gaps

There is little information on how Danish consumers are exposed to n-hexane and if certain product

types, e.g. for car repair and maintenance, may result in unacceptable exposures.


7. Information on alternatives

7.1 Identification of possible alternatives

The following sections discuss possible alternatives of n-hexane in its main uses.

7.1.1 Alternatives to n-hexane in solvent extraction

The first industrial operations in Europe of solvent extraction of editable oils were established in

1870. Carbon disulphide was the first patented solvent but other used solvents were petroleum

naphthas, trichloroethylene, and ethanol. The use of trichloroethylene stayed in the US at least until

the 1950s but there were problems with cattle dying of a “bloody nose disease” when fed with the

product. At that time the purer solvents, distilled with a narrow distillation range, became available,

and n-hexane rich solvents became the solvent of choice. Although alternatives to hexane for sol-

vent extraction of oil seeds have been investigated for decades it is still the major solvent in use.

Catastrophic explosions have occurred during time due to the high flammability of hexane and since

the 1970's more focus has been on the health and environmental effects of n-hexane. In December

2007 there was a large explosion in Aarhus from hexane used for solvent extraction. Such incidents

and the hazards to human health and the environment have pushed for substitution consideration.

Important properties of the solvent to be used include vaporization temperature, boiling point, oil

solubility, viscosity, specific gravity, polarity, reactivity, purity and stability to heat, light and water.

As the solvent is recycled, it must withstand repeated cycles of heating, vaporisation and cooling.

Stability is also required to prevent contamination of meal and oil with potentially hazardous de-

composition products (Johnson & Lusas, 1983). n-Hexane is characterised by low vaporization

temperature, high stability, low corrosiveness and low greasy residual effects and has therefore

from a technical point of view been an excellent choice (Anderson G.E., 2011).

Research on alternative solvents has suggested ethanol, isopropanol, methylene chloride, aqueous

acetone, and hexane/acetone/water mixtures but it seems that it is difficult to find a replacement

that has the same ability to produce a high-quality edible oil (colour, taste and other food proper-

ties).

Various alcohols, e.g. isopropyl alcohol or a 3:2 mixture of hexane and isopropyl alcohol are alterna-

tives that have been tested.

Solvents that are allowed to be used for extraction in relation to food and food ingredients according

to the current legislation in EU are shown in Table 17.


TABLE 17

EXTRACTION SOLVENTS ALLOWED IN FOOD OR RAW MATERIAL PROCESSING (2009/32/EC)

Solvents with no restrictions Solvents for which conditions of use are speci-

fied

Propane

Butane

Ethyl acetate

Ethanol

Carbon dioxide

Acetone

Nitrous oxide

Hexane

Methyl acetate

Ethylmethylketone

Dichloromethane

Methanol

Propan-1-ol

Propan-2-ol

Diethyl ether

Cyclohexane

Methyl acetate

Butan-1-ol

Butan-2-o

1,1,1,2-tetrafluoroethane

Other, more recent studies suggest Soft Aqueous Processing which is a low temperature extraction

method with the use of enzymes and fractionation using membranes. Such methods make the use of

organic solvents for extraction superfluous or reduce the amounts to be used (Parmentier, 2006 a).

Multi-enzyme hydrolysis as a pre-treatment option to improve solvent extraction and its eventual

adaptation to conventional processes has been tested in relation to extraction of soybean oil (Grasso

et al., 2012). I was concluded that that enzymatic hydrolysis is a pre-treatment option that could be

incorporated into the current processes of soybean oil solvent extraction. The improvements ob-

tained could be applied at industrial level and result in faster extraction processes, higher oil yield

and/or decreased amount of solvent used. Many other studies investigating the application of en-

zymatic hydrolysis of oilseeds can be found in the literature.

It appears that research and development efforts are still being carried out to find the proper meth-

odology and optimum processing parameters (for example, solvent, pH, temperature, enzymatic

concentration, hydrolysis period) that will enhance both the oil availability and extractability. Also

aqueous enzymatic extraction is studied as another promising technique where hydrothermal pre-

treatment is given prior to oil extraction to activate the native enzymes present in the oilseeds and

to loosen their structure for the extraction of extra oil with better quality (Ghosh et al., 2007).

It is mentioned in one of the Danish environmental permits for a solvent extraction plant that for

the sake of the quality of the final edible oils there is no good alternative to hexane for the oil seed

extraction performed.

For the production of bio diesel from vegetable oils, in-situ transesterification eliminates the hexane

extraction process. In that kind of process, alcohol serves both as an extracting agent for the oils

from the seeds and as a reagent for alkyl esters production. In situ transesterification offers the

advantages of substituting hexane and minimizing oil losses.

7.1.2 Alternatives to n-hexane in laboratories

Ethoxynonafluorobutane is a substitute for n-hexane in normal-phase high-performance liquid

chromatographic separations. One difficulty with substitution is that n-hexane is specified in many

laboratory standards (Kagan, 2001).


7.1.3 Alternatives to n-hexane as a blowing agent

Substitution among physical blowing agents will depend upon equipment design for liquid vs gas

blowing agent, explosion-proof status, solubility of the blowing agent in molten and cooled polymer

foam, and the rate and consequences of diffusion of the agent from the finished foam (Acton (Ed),

2013).

Depending upon the specific equipment and conditions, iso-pentane or iso-hexane might be the

closest substitutes for n-hexane in this application. It is expected that this use of n-hexane is limited

to very specialized foam products.

7.1.4 Alternatives to n-hexane as a reaction medium

The polyethylene and polypropylene processes which use n-hexane as either the reaction solvent or

the liquid phase for slurry reactions are highly specific to n-hexane due to the specific combination

of solubility, boiling range and chemical stability. One of the polypropylene processes may be able

to use heptane in combination with or to replace hexane. However, there are no polyethylene or

polypropylene plants in Denmark.

7.1.5 Alternatives to n-hexane as special purpose solvent and cleaning agent (de-

greaser)

Water-based cleaners, both for industrial, professional and domestic use, will most often be availa-

ble, but require a different technique and sometimes also new equipment.

Many large companies have developed solvent selection and replacement guides to be used in rela-

tion to purchasing of products and production planning. In such guides n-hexane is often is listed as

a substance to avoid or restrict and substitute with e.g. heptane6 if possible.

In the printing industry, vegetable oil-based cleaners can sometimes be used instead of hexane

(IRTA, 2006).

Adhesives for the shoe manufacturing industry typically contained large amounts of n-hexane. The

n-hexane has been partly substituted during the past 30 years with substances like ethyl acetate,

cyclohexane, hexane isomers, methyl ethyl ketone, heptane and acetone (US NIH, 2014).

7.1.6 Hazard classification of suggested alternatives

The hazard classifications of the substances suggested as alternatives to n-hexane in the different

application areas are shown in Table 18. Alternatives that are not identified by CAS number or

chemical name are not included, e.g. vegetable oils and enzymes suggested for pre-treatment to

improve solvent extraction. Suggested mixtures of the listed substances are also not included in the

table.

All suggested substances except methylene chloride are classified as highly flammable. Although

their flash points are not identical, they are not directly safer alternatives with regard to flammabil-

ity.

Methylene chloride is not flammable but is classified for carcinogenicity with Carc.2 (Suspected of

causing cancer) and thereby not an attractive alternative with regard to health hazard and the re-

quirements that follow according to occupational health and safety legislation. Only ethanol is not

classified for any health or environmental hazards.

6 Example of solvent substitution guide: http://safety.dept.shef.ac.uk/chemical/Solvent%20Substitution.pdf

http://safety.dept.shef.ac.uk/chemical/Solvent%20Substitution.pdf


TABLE 18

CLASSIFICATION OF SUGGESTED ALTERNATIVES TO N-HEXANE

Substance name CAS no. Suggested application area Hazard Class and Category

Code(s) and Hazard State-

ment Codes

Pictograms

Harmonised classifications

Acetone 67-64-1 Solvent extraction

Special purpose solvent

Cleaning agent

Flam - Liq. 2; H225

Eye Irrit. 2; H319

STOT SE 3;H336

Cyclohexane 110-82-7 Special purpose solvent

Cleaning agent

Flam. Liq. 2; H225

Asp. Tox- 1; H304

Skin Irrit. 2; H315

STOT SE 3;H336

Aquatic Acute 1; H400

Aquatic Chronic 1; H410

Ethanol 64-17-5 Solvent extraction Flam. Liq. 2; H225

Ethyl acetate 141-78-6 Special purpose solvent

Cleaning agent

Flam. Liq. 2; H225

Eye Irrit. 2; H319

STOT SE 3;H336

Heptane 142-82-5 Reaction medium


Cleaning agent

Flam. Liq. 2; H225

Asp. Tox- 1; H304

Skin Irrit. 2; H315

STOT SE 3;H336

Aquatic Acute 1; H400


Isopropyl alcohol 67-63-0 Solvent extraction Flam. Liq. 2; H225

Eye Irrit. 2; H319

STOT SE 3;H336

Iso-hexane 107-83-5 Solvent extraction

Blowing agent


Cleaning agent

Flam. Liq. 2; H225

Asp. Tox- 1; H304

STOT SE 3;H336


Iso-pentane 78-78-4 Blowing agent Flam.- Liq. 1; H224

Asp- Tox- 1; H304

Skin Irrit. 2; H315

STOT SE 3;H336


Methylene chlo-

ride

75-09-2 Solvent extraction Carc. 2;H351

Methyl ethyl ke-

tone

78-93-3 Special purpose solvent

Cleaning agent

Flam. Liq. 2; H225

Eye Irrit. 2; H319

STOT SE 3;H336

Industry classifications


Substance name CAS no. Suggested application area Hazard Class and Category

Code(s) and Hazard State-

ment Codes

Pictograms

Ethoxynonafluo-

ro-butane

163702-05-4 Laboratory Flam - Liq. 2; H225 (22)*

Skin Irrit. 2; H315 (23) *

Eye Irrit. 2; H319 (23) *

STOT SE 3;H335 (23) *

*: Number of notifiers of the hazard class shown in brackets.

7.2 Historical Trends and Future Trends

Other solvents have substituted the use of n-hexane in many consumer products or the n-hexane

containing products have been replaced with other chemical-type products that are water-based.

The large-scale uses of n-hexane in Denmark for solvent extraction and as reaction solvent in the

production of insecticides do not seem to decrease as these processes depend on the technical prop-

erties of the solvent. These uses are in closed systems.

7.3 Summary and Conclusions

The high volume uses in Denmark are based on n-hexane rich blends of hexane isomers and it does

not seem likely that the n-hexane will be replaced for these applications in the near future. For

solvent extraction of edible oils, only solvents that are allowed according to the legislation in this

area can be used.

Many large companies have developed solvent selection and replacement guides where n-hexane

often is listed as a substance to avoid or restrict where technical requirements makes it possible.

With regard to consumer products, n-hexane has been substituted in many products before the turn

of the millennium and n-hexane is mostly found in smaller concentrations in the majority of the

products. For most of the consumer product type alternatives will be available without hexane.

As indicated in Table 18, most of the identified alternatives are also highly flammable and are not

safer alternatives with respect to flammability. Heptane, which is often suggested as an alternative

has a stronger environmental classification and may therefore be a concern in relation to uses such

as cleaning and washing. From a health perspective several of the alternatives share some of the less

critical health effects of n-hexane. Ethanol, which is the least toxic of the alternatives, has been

tested as an extraction solvent, but a technological solution is not available.


8. Abbreviations and acro-nyms

ASTDR Agency for Toxic Substances and Disease Registry

BCF Bioconcentration factor

BTX Benzene, toluene, and xylene

CLP Classification, Labelling and Packaging Regulation

DT Degradation time

ECHA European Chemicals Agency

EFSA European Food Safety Authority

EPA Environmental Protection Agency

EU European Union

HELCOM The Baltic Marine Environment Protection Commission (Helsinki Commission)

HSPA Hydrocarbon Solvents Producers Association

Kow Octanol/water partitioning coefficient

Koc Organic carbon/water partitioning coefficient

Kp Partial pressure equilibrium constant

LC Lethal effect concentration

LNAPL Light non-aqueous phase liquid

LOUS List of Undesirable Substances (of the Danish EPA)

NIH National Institute of Health

NPI National Pollutant Inventory

NOAEL No observable adverse effect level

NOEC No observable effect concentration

NOVANA Danish national monitoring and assessment programme

OECD Organisation for Economic Co-operation and Development

OSPAR Convention for the Protection of the Marine Environment of the North-East Atlantic

PEC Predicted environmental concentration

PNEC Predicted no effect concentration

QSAR Quantitative Structure and Activity Relationship

REACH Registration, Evaluation, Authorisation and Restriction of Chemicals

STP Sewage treatment plant

SVHC Substance of Very High Concern

UVCB Substances of Unknown or Variable composition, Complex reaction products or Bio-

logical materials



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Appendix 1: Background information to chapter 2 on legal framework

The following annex provides some background information on subjects addressed in Chapter 3.

The intention is that the reader less familiar with the legal context may read this concurrently with

chapter 3.

EU and Danish legislation

Chemicals are regulated via EU and national legislations, the latter often being a national transposi-

tion of EU directives.

There are four main EU legal instruments:

Regulations (DK: Forordninger) are binding in their entirety and directly applicable in all EU

Member States.

Directives (DK: Direktiver) are binding for the EU Member States as to the results to be

achieved. Directives have to be transposed (DK: gennemført) into the national legal framework

within a given timeframe. Directives leave margin for manoeuvering as to the form and means

of implementation. However, there are great differences in the space for manoeuvering be-

tween directives. For example, several directives regulating chemicals previously were rather

specific and often transposed more or less word-by-word into national legislation. Consequent-

ly and to further strengthen a level playing field within the internal market, the new chemicals

policy (REACH) and the new legislation for classification and labelling (CLP) were implement-

ed as Regulations. In Denmark, Directives are most frequently transposed as laws (DK: love)

and statutory orders (DK: bekendtgørelser).

The European Commission has the right and the duty to suggest new legislation in the form of regu-

lations and directives. New or recast directives and regulations often have transitional periods for

the various provisions set-out in the legal text. In the following, we will generally list the latest piece

of EU legal text, even if the provisions identified are not yet fully implemented. On the other hand,

we will include currently valid Danish legislation, e.g. the implementation of the cosmetics di-

rective) even if this will be replaced with the new Cosmetic Regulation.

Decisions are fully binding on those to whom they are addressed. Decisions are EU laws relat-

ing to specific cases. They can come from the EU Council (sometimes jointly with the European

Parliament) or the European Commission. In relation to EU chemicals policy, decisions are

e.g. used in relation to inclusion of substances in REACH Annex XVII (restrictions). This takes

place via a so-called comitology procedure involving Member State representatives. Decisions

are also used under the EU ecolabelling Regulation in relation to establishing ecolabel criteria

for specific product groups.

Recommendations and opinions are non-binding, declaratory instruments.

In conformity with the transposed EU directives, Danish legislation regulate to some extent chemi-

cals via various general or sector specific legislation, most frequently via statutory orders (DK:

bekendtgørelser).

Chemicals legislation

REACH and CLP

The REACH Regulation7 and the CLP Regulation8 are the overarching pieces of EU chemicals legis-

lation regulating industrial chemicals. The below will briefly summarise the REACH and CLP provi-

7 Regulation (EC) No 1907/2006 concerning the Registration, Evaluation, Authorisation and Restriction of Chemicals (REACH)

8 Regulation (EC) No 1272/2008 on classification, labelling and packaging of substances and mixtures


sions and give an overview of 'pipeline' procedures, i.e. procedures which may (or may not) result in

an eventual inclusion under one of the REACH procedures.

(Pre-)Registration

All manufacturers and importers of chemical substance > 1 tonne/year have to register their chemi-

cals with the European Chemicals Agency (ECHA). Pre-registered chemicals benefit from tonnage

and property dependent staggered dead-lines:

30 November 2010: Registration of substances manufactured or imported at 1000 tonnes or

more per year, carcinogenic, mutagenic or toxic to reproduction substances above 1 tonne per

year, and substances dangerous to aquatic organisms or the environment above 100 tonnes per

year.

31 May 2013: Registration of substances manufactured or imported at 100-1000 tonnes per

year.

31 May 2018: Registration of substances manufactured or imported at 1-100 tonnes per year.

Evaluation

A selected number of registrations will be evaluated by ECHA and the EU Member States. Evalua-

tion covers assessment of the compliance of individual dossiers (dossier evaluation) and substance

evaluations involving information from all registrations of a given substance to see if further EU

action is needed on that substance, for example as a restriction (substance evaluation).

Authorisation

Authorisation aims at substituting or limiting the manufacturing, import and use of substances of

very high concern (SVHC). For substances included in REACH annex XIV, industry has to cease use

of those substance within a given deadline (sunset date) or apply for authorisation for certain speci-

fied uses within an application date.

Restriction

If the authorities assess that that there is a risks to be addressed at the EU level, limitations of the

manufacturing and use of a chemical substance (or substance group) may be implemented. Re-

strictions are listed in REACH annex XVII, which has also taken over the restrictions from the pre-

vious legislation (Directive 76/769/EEC).

Classification and Labelling

The CLP Regulation implements the United Nations Global Harmonised System (GHS) for classifi-

cation and labelling of substances and mixtures of substances into EU legislation. It further speci-

fies rules for packaging of chemicals.

Two classification and labelling provisions are:

1. Harmonised classification and labelling for a number of chemical substances. These classi-

fications are agreed at the EU level and can be found in CLP Annex VI. In addition to newly agreed

harmonised classifications, the annex has taken over the harmonised classifications in Annex I of

the previous Dangerous Substances Directive (67/548/EEC); classifications which have been 'trans-

lated' according to the new classification rules.

2. Classification and labelling inventory. All manufacturers and importers of chemicals sub-

stances are obliged to classify and label their substances. If no harmonised classification is availa-

ble, a self-classification shall be done based on available information according to the classification

criteria in the CLP regulation. As a new requirement, these self-classifications should be notified to

ECHA, which in turn publish the classification and labelling inventory based on all notifications

received. There is no tonnage trigger for this obligation. For the purpose of this report, self-

classifications are summarised in Appendix 2 to the main report.


Ongoing activities - pipeline

In addition to listing substance already addressed by the provisions of REACH (pre-registrations,

registrations, substances included in various annexes of REACH and CLP, etc.), the ECHA web-site

also provides the opportunity for searching for substances in the pipeline in relation to certain

REACH and CLP provisions. These will be briefly summarised below:

Community Rolling Action Plan (CoRAP)

The EU member states have the right and duty to conduct REACH substance evaluations. In order

to coordinate this work among Member States and inform the relevant stakeholders of upcoming

substance evaluations, a Community Rolling Action Plan (CoRAP) is developed and published,

indicating by who and when a given substance is expected to be evaluated.

Authorisation process; candidate list, Authorisation list, Annex XIV

Before a substance is included in REACH Annex XIV and thus being subject to Authorisation, it has

to go through the following steps:

1. It has to be identified as a SVHC leading to inclusion in the candidate list9

2. It has to be prioritised and recommended for inclusion in ANNEX XIV (These can be found as

Annex XIV recommendation lists on the ECHA web-site)

3. It has to be included in REACH Annex XIV following a comitology procedure decision (sub-

stances on Annex XIV appear on the Authorisation list on the ECHA web-site).

The candidate list (substances agreed to possess SVHC properties) and the Authorisation list are

published on the ECHA web-site.

Registry of intentions

When EU Member States and ECHA (when required by the European Commission) prepare a pro-

posal for:

a harmonised classification and labelling,

an identification of a substance as SVHC, or

a restriction.

This is done as a REACH Annex XV proposal.

The 'registry of intentions' gives an overview of intensions in relation to Annex XV dossiers divided

into:

current intentions for submitting an Annex XV dossier,

dossiers submitted, and

withdrawn intentions and withdrawn submissions

for the three types of Annex XV dossiers.

International agreements

OSPAR Convention

OSPAR is the mechanism by which fifteen Governments of the western coasts and catchments of

Europe, together with the European Community, cooperate to protect the marine environment of

the North-East Atlantic.

9 It should be noted that the candidate list is also used in relation to articles imported to, produced in or distributed in the EU.

Certain supply chain information is triggered if the articles contain more than 0.1% (w/w) (REACH Article 7.2 ff).


Work to implement the OSPAR Convention and its strategies is taken forward through the adoption

of decisions, which are legally binding on the Contracting Parties, recommendations and other

agreements. Decisions and recommendationsset out actions to be taken by the Contracting Parties.

These measures are complemented by other agreements setting out:

issues of importance

agreed programmes of monitoring, information collection or other work which the Contracting

Parties commit to carry out.

guidelines or guidance setting out the way that any programme or measure should be imple-

mented

actions to be taken by the OSPAR Commission on behalf of the Contracting Parties.

HELCOM - Helsinki Convention

The Helsinki Commission, or HELCOM, works to protect the marine environment of the Baltic Sea

from all sources of pollution through intergovernmental co-operation between Denmark, Estonia,

the European Community, Finland, Germany, Latvia, Lithuania, Poland, Russia and Sweden. HEL-

COM is the governing body of the "Convention on the Protection of the Marine Environment of the

Baltic Sea Area" - more usually known as the Helsinki Convention.

In pursuing this objective and vision the countries have jointly pooled their efforts in HEL-

COM, which is works as:

an environmental policy maker for the Baltic Sea area by developing common environmental

objectives and actions;

an environmental focal point providing information about (i) the state of/trends in the marine

environment; (ii) the efficiency of measures to protect it and (iii) common initiatives and posi-

tions which can form the basis for decision-making in other international fora;

a body for developing, according to the specific needs of the Baltic Sea, Recommendations of

its own and Recommendations supplementary to measures imposed by other international or-

ganisations;

a supervisory body dedicated to ensuring that HELCOM environmental standards are fully

implemented by all parties throughout the Baltic Sea and its catchment area; and

a co-ordinating body, ascertaining multilateral response in case of major maritime incidents.

CLRTAP - Convention on Long-range Transboundary Air Pollution

Since 1979 the Convention on Long-range Transboundary Air Pollution (CLRTAP) has addressed

some of the major environmental problems of the UNECE (United Nations Economic Commission

for Europe) region through scientific collaboration and policy negotiation.

The aim of the Convention is that Parties shall endeavour to limit and, as far as possible, gradually

reduce and prevent air pollution including long-range transboundary air pollution. Parties develop

policies and strategies to combat the discharge of air pollutants through exchanges of information,

consultation, research and monitoring.

The Convention has been extended by eight protocols that identify specific measures to be taken by

Parties to cut their emissions of air pollutants. Three of the protocols specifically address the emis-

sion of hazardous substances of which some are included in LOUS:

The 1998 Protocol on Persistent Organic Pollutants (POPs); 33 Parties. Entered into force on

23 October 2003.

The 1998 Protocol on Heavy Metals; 33 Parties. Entered into force on 29 December 2003.

The 1991 Protocol concerning the Control of Emissions of Volatile Organic Compounds or their

Transboundary Fluxes; 24 Parties. Entered into force 29 September 1997.

http://www.ospar.org/content/content.asp?menu=00330110000040_000000_000000

http://www.ospar.org/v_measures/browse.asp?menu=00530418000000_000000_000000

http://www.helcom.fi/Convention/en_GB/convention/


Stockholm Convention on Persistent Organic Pollutants (POPs)

The Stockholm Convention on Persistent Organic Pollutants is a global treaty to protect human

health and the environment from chemicals that remain intact in the environment for long periods,

become widely distributed geographically, accumulate in the fatty tissue of humans and wildlife,

and have adverse effects to human health or to the environment. The Convention is administered

by the United Nations Environment Programme and is based in Geneva, Switzerland.

Rotterdam Convention

The objectives of the Rotterdam Convention are:

to promote shared responsibility and cooperative efforts among Parties in the international

trade of certain hazardous chemicals in order to protect human health and the environment

from potential harm;

to contribute to the environmentally sound use of those hazardous chemicals, by facilitating

information exchange about their characteristics, by providing for a national decision-making

process on their import and export and by disseminating these decisions to Parties.

The Convention creates legally binding obligations for the implementation of the Prior In-

formed Consent (PIC) procedure. It built on the voluntary PIC procedure, initiated by UNEP

and FAO in 1989 and ceased on 24 February 2006.

The Convention covers pesticides and industrial chemicals that have been banned or severely re-

stricted for health or environmental reasons by Parties and which have been notified by Parties for

inclusion in the PIC procedure. One notification from each of two specified regions triggers consid-

eration of addition of a chemical to Annex III of the Convention. Severely hazardous pesticide for-

mulations that present a risk under conditions of use in developing countries or countries with

economies in transition may also be proposed for inclusion in Annex III.

Basel Convention

The Basel Convention on the Control of Transboundary Movements of Hazardous Wastes and their

Disposal was adopted on 22 March 1989 by the Conference of Plenipotentiaries in Basel, Switzer-

land, in response to a public outcry following the discovery, in the 1980s, in Africa and other parts

of the developing world of deposits of toxic wastes imported from abroad.

The overarching objective of the Basel Convention is to protect human health and the environment

against the adverse effects of hazardous wastes. Its scope of application covers a wide range of

wastes defined as “hazardous wastes” based on their origin and/or composition and their character-

istics, as well as two types of wastes defined as “other wastes” - household waste and incinerator

ash.

The provisions of the Convention center around the following principal aims:

the reduction of hazardous waste generation and the promotion of environmentally sound

management of hazardous wastes, wherever the place of disposal;

the restriction of transboundary movements of hazardous wastes except where it is perceived

to be in accordance with the principles of environmentally sound management; and

a regulatory system applying to cases where transboundary movements are permissible.

Eco-labels

Eco-label schemes are voluntary schemes where industry can apply for the right to use the eco-label

on their products if these fulfil the ecolabelling criteria for that type of product. An EU scheme (the

flower) and various national/regional schemes exist. In this project we have focused on the three

most common schemes encountered on Danish products.

http://www.pops.int/


EU flower

The EU ecolabelling Regulation lays out the general rules and conditions for the EU ecolabel; the

flower. Criteria for new product groups are gradually added to the scheme via 'decisions'; e.g. the

Commission Decision of 21 June 2007 establishing the ecological criteria for the award of the

Community eco-label to soaps, shampoos and hair conditioners.

Nordic Swan

The Nordic Swan is a cooperation between Denmark, Iceland, Norway, Sweden and Finland. The

Nordic Ecolabelling Board consists of members from each national Ecolabelling Board and decides

on Nordic criteria requirements for products and services. In Denmark, the practical implementa-

tion of the rules, applications and approval process related to the EU flower and Nordic Swan is

hosted by Ecolabelling Denmark "Miljømærkning Danmark" (http://www.ecolabel.dk/). New crite-

ria are applicable in Denmark when they are published on the Ecolabelling Denmark’s website (ac-

cording to Statutory Order no. 447 of 23/04/2010).

Blue Angel (Blauer Engel)

The Blue Angel is a national German eco-label. More information can be found on:

http://www.blauer-engel.de/en.

http://www.blauer-engel.de/en

Strandgade 29

1401 Copenhagen K, Denmark

Tel.: (+45) 72 54 40 00

www.mst.dk

Survey of n-hexan

This survey is part of the Danish EPA’s review of the substances on the List of Undesirable Substances

(LOUS). The survey concerns the aliphatic organic substance n-hexan. This substance was included in

the LOUS list in 1999. The report defines the substance and present information on the use and occur-

rence of n-hexan internationally and in Denmark, information on existing regulation, on environmental

and health effects, on monitoring and exposure, on waste management and on alternatives to the sub-

stance.

Denne kortlægning er et led i Miljøstyrelsens kortlægninger af stofferne på Listen Over Uønskede Stoffer

(LOUS). Kortlægningen omhandler det alifatiske organiske stof n-hexan. Rapporten definerer stoffet og

indeholder blandt andet en beskrivelse af brugen og forekomsten af styren internationalt og i Danmark,

om eksisterende regulering, en beskrivelse af miljø- og sundhedseffekter af stoffet, af moniteringsdata, af

affaldsbehandling samt alternativer til stoffet.